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  • Theoretical, Physical and Computational Chemistry  (1,576)
  • 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
  • 05. General::05.09. Miscellaneous::05.09.99. General or miscellaneous
  • Bacteria
  • Wiley-Blackwell  (1,597)
  • Istituto Nazionale di Geofisica e Vulcanologia  (16)
  • American Chemical Society
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  • 1
    Publication Date: 2022-05-27
    Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Gosselin, K. M., Nelson, R. K., Spivak, A. C., Sylva, S. P., Van Mooy, B. A. S., Aeppli, C., Sharpless, C. M., O’Neil, G. W., Arrington, E. C., Reddy, C. M., & Valentine, D. L. Production of two highly abundant 2-methyl-branched fatty acids by blooms of the globally significant marine cyanobacteria Trichodesmium erythraeum. ACS Omega, 6(35), (2021): 22803–22810, https://doi.org/10.1021/acsomega.1c03196.
    Description: The bloom-forming cyanobacteria Trichodesmium contribute up to 30% to the total fixed nitrogen in the global oceans and thereby drive substantial productivity. On an expedition in the Gulf of Mexico, we observed and sampled surface slicks, some of which included dense blooms of Trichodesmium erythraeum. These bloom samples contained abundant and atypical free fatty acids, identified here as 2-methyldecanoic acid and 2-methyldodecanoic acid. The high abundance and unusual branching pattern of these compounds suggest that they may play a specific role in this globally important organism.
    Description: This work was funded with grants from the National Science Foundation grants OCE-1333148, OCE-1333162, and OCE-1756254 and the Woods Hole Oceanographic Institution (IR&D). GCxGC analysis made possible by WHOI’s Investment in Science Fund.
    Keywords: Lipids ; Alkyls ; Bacteria ; Genetics ; Chromatography
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
    Publication Date: 2017-04-04
    Description: Seismological, geological and geodetic data have been integrated to characterize the seismogenic structure of the late 2013-early 2014 moderate energy (maximum local magnitude MLmax = 4.9) seismic sequence that struck the interior of the Matese Massif, part of the Southern Apennines active extensional belt. The sequence, heralded by a ML = 2.7 foreshock, was characterized by two main shocks with ML = 4.9 and ML = 4.2, respectively, which occurred at a depth of ∼17–18 km. The sequence was confined in the 10–20 km depth range, significantly deeper than the 1997–1998 sequence which occurred few km away on the northeastern side of the massif above ∼15 km depth. The depth distribution of the 2013–14 sequence is almost continuous, albeit a deeper (16–19 km) and a shallower (11–15 km) group of events can be distinguished, the former including the main shocks and the foreshock. The epicentral distribution formed a ∼10 km long NNW–SSE trending alignment, which almost parallels the surface trace of late Pliocene–Quaternary southwest-dipping normal faults with a poor evidence of current geological and geodetic deformation. We built an upper crustal model profile for the eastern Matese massif through integration of geological data, oil exploration well logs and seismic tomographic images. Projection of hypocentres on the profile suggests that the seismogenic volume falls mostly within the crystalline crust and subordinately within the Mesozoic sedimentary cover of Apulia, the underthrust foreland of the Southern Apennines fold and thrust belt. Geological data and the regional macroseismic field of the sequence suggest that the southwest-dipping nodal plane of the main shocks represents the rupture surface that we refer to here as the Matese fault. The major lithological discontinuity between crystalline and sedimentary rocks of Apulia likely confined upward the rupture extent of the Matese fault. Repeated coseismic failure represented by the deeper group of events in the sequence, activated in a passive fashion the overlying ∼11–15 km deep section of the upper crustal normal faults. We consider the southwest-dipping Matese fault representative of a poorly known type of seismogenic structures in the Southern Apennines, where extensional seismogenesis and geodetic strain accumulation occur more frequently on NE-dipping, shallower-rooted faults. This is the case of the Boiano Basin fault located on the northern side of the massif, to which the 1997–1998 sequence is related. The close proximity of the two types of seismogenic faults at the Matese Massif is related to the complex crustal architecture generated by the Pliocene–early Pleistocene contractional and transpressional tectonics.
    Description: Published
    Description: 823-837
    Description: 2T. Tettonica attiva
    Description: JCR Journal
    Description: partially_open
    Keywords: Seismicity and tectonics ; Continental tectonics: extensional ; Crustal structure ; 04. Solid Earth::04.04. Geology::04.04.01. Earthquake geology and paleoseismology ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 3
    Publication Date: 2017-04-04
    Description: Mt. Vesuvius (southern Italy) is one of the most hazardous volcanoes in the world. Its activity is currently characterized by moderate seismicity, with hypocenters located beneath the crater zone with depth rarely exceeding 5 km and magnitudes generally less than 3. The current configu- ration of the seismic monitoring network of Mt. Vesuvius consists of 18 seismic stations and 7 infrasound microphones. During the period 2006- 2010 a seismic array with 48 channels was also operative. The station distribution provides appropriate coverage of the area around the volcanic edifice. The current development of the network and its geometry, under conditions of low seismic noise, allows locating seismic events with M〈1. Remote instruments continuously transmit data to the main acquisition center in Naples. Data transmission is realized using different technological solutions based on UHF, Wi-Fi radio links, and TCP/IP client-server applications. Data are collected in the monitoring center of the Osservatorio Vesuviano (Italian National Institute of Geophysics and Volcanology, Naples section), which is equipped with systems for displaying and analyzing signals, using both real-time automatic and manual procedures. 24-hour surveillance allows to immediately communicate any significant anomaly to the Civil Protection authorities.
    Description: Published
    Description: S0450
    Description: 5V. Sorveglianza vulcanica ed emergenze
    Description: 1IT. Reti di monitoraggio e Osservazioni
    Description: JCR Journal
    Description: open
    Keywords: Vesuvius ; seismic network ; volcano monitoring ; network performance ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 4
    Publication Date: 2017-04-04
    Description: Until a decade ago, regression analyses for conversions between different types of magnitude were using only the ordinary least squares method,which assumes that the independent variable is error free, or the simple orthogonal regression method,which assumes equal uncertainties for the two variables. The recent literature became aware of the inadequacy of such approaches and proposes the use of general orthogonal regression methods that account for different uncertainties of the two regression variables. Under the common assumption that only the variance ratio η between the dependent and independent variables is known, we compared three of such general orthogonal regression methods that have been applied to magnitude conversions: the chi-square regression, the general orthogonal regression, and the weighted total least squares. Although their formulations might appear quite different, we show that, under appropriate conditions, they all compute almost exactly the same regression coefficients and very similar (albeit slightly different) formal uncertainties. The latter are in most cases smaller than those estimated by bootstrap simulation but the amount of the deviation depends on the data set and on the assumed variance ratio.
    Description: European Union project SHARE (Seismic Hazard Harmonization in Europe) within the ambit of Task 3.1‘European Earthquake Database’.
    Description: Published
    Description: 1135-1151
    Description: JCR Journal
    Description: restricted
    Keywords: Earthquake source observations; Statistical seismology ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 5
    Publication Date: 2017-04-04
    Description: In 2012 two seismic surveys were carried out in the area of Bagnolifutura (Campi Flegrei, Naples), with the aim of characterizing the properties of the seismic noise during the drilling activity performed in the framework of the Campi Flegrei Deep Drilling Project (CFDDP; https://sites.google.com/site/cfddpproject/). During the first survey, which was conducted from 2 to 4 April, before the drilling, seven broadband three-component seismometers were installed in two different array configurations. The second survey started on November 26, in concomitance with the drilling operations and fluid injection, and ended on December 5, four days after the end of the drilling, when the maximum depth of 502 m was reached. During this period seven broadband and one short-period three-component sensors were installed. A preliminary spectral analysis was performed on samples of seismic noise; moreover the root mean square of the amplitude of the signals and the polarization parameters were calculated. The preliminary results show similar spectral and polarization features for the data of the two surveys, whereas the amplitude of the seismic noise collected during the second survey is greatly influenced by the bad meteorological conditions. As future development experimental site transfer functions from Nakamura’s technique and surface wave dispersion from array techniques will be calculated to obtain the shallow crustal structure. The results corresponding to the different phases of the drilling activity will be compared, with the aim of establishing if significant variations of the medium properties have occurred during the experiment. Moreover the recorded signals will be deeply investigated in order to detect the eventual occurrence of microseismicity induced by fluid injection and to define its features.
    Description: Published
    Description: 1-18
    Description: N/A or not JCR
    Description: open
    Keywords: Campi Flegrei ; seismic noise ; array techniques ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 6
    Publication Date: 2017-04-04
    Description: In the 1980's, from an analysis of satellite images, Russian scientists reported on a short-term thermal infrared radiation enhancement that occurred before some medium-to-large earthquakes in central Asia [Gorny et al. 1988]. Since then, many researchers have been studying earthquake thermal anomalies with satellite remote sensing data [Qiang et al. 1991, Tronin 1996, Tramutoli et al. 2001, Ouzounov and Freund 2004, Saraf and Choudhury 2004, Aliano et al. 2008, Blackett et al. 2011]. Recently, abnormal surface latent heat flux [Dey and Singh 2003, Cervone et al. 2005, Qin et al. 2009, Qin et al. 2011, Qin et al. 2012], outgoing long-wave radiation [Ouzounov et al. 2007] and microwave radiation [Takashi and Tadashi 2010] have also been shown to precede earthquakes. To investigate the possible physical mechanisms of such satellite thermal anomalies, some studies conducted a series of detecting experiments on rock loaded to fracturing [Wu et al. 2000, Freund 2002, Wu et al. 2002, Wu et al. 2006a, Wu et al. 2006b, Freund et al. 2007], and some hypotheses have been proposed. These have included: leaking of pore-gas, and hence the resulting greenhouse effect [Qiang et al. 1995]; activating and recombining of p-holes during rock deformation [Freund 2002]; release of latent heat due to near-surface air ionization [Pulinets et al. 2006], and stress-induced thermal effects due to friction and fluids [Wu and Liu 2009]. According to the Istituto Nazionale di Geofisica e Vulcanologia (INGV; National Institute of Geophysics and Volcanology), two major earthquakes with almost the same large magnitudes struck northern Italy, on the Po Plain in the Emilia Region. The first hit on May 20, 2012, at 02:03 UTC, with ML 5.9 (44.89 °N, 11.23 °E; 6 km in depth), and the second on May 29, 2012, at 07:00 UTC, with ML 5.8 (44.85 °N, 11.09 °E; 10 km in depth). These caused a total of 27 deaths and widespread damage. In this study, the long-term temperature data from both satellite and ground (with greater emphasis on the satellite data) have been used to determine whether there were thermal anomalies associated with this Emilia 2012 seismic sequence. In particular, the next section will be dedicated to describing both the data and the method of analysis. In Section 3, we provide the more significant results, which we discuss in Section 4, together with the main conclusions. We acknowledge that this work cannot be exhaustive, as it will require more data and analyses. However, although further studies will be welcome, we are confident that we have done the best with the data at our disposal.
    Description: Published
    Description: 823-828
    Description: 1.10. TTC - Telerilevamento
    Description: 3.1. Fisica dei terremoti
    Description: JCR Journal
    Description: open
    Keywords: earthquake event ; numerical method ; surface temperature ; Emilia-Romagna, Italy ; Emilia ; 04. Solid Earth::04.02. Exploration geophysics::04.02.05. Downhole, radioactivity, remote sensing, and other methods ; 04. Solid Earth::04.06. Seismology::04.06.01. Earthquake faults: properties and evolution ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 7
    Publication Date: 2021-03-01
    Description: On September 6, 2002, at 01:21 GMT, the western part of the Tyrrhenian coast of Sicily was hit by an earthquake of magnitude ML = 5.6, representing the mainshock of a seismic sequence of roughly 500 earthquakes recorded in about one month. The event, although characterized by a moderate magnitude and located some forty kilometres offshore, produced relevant macroseismic effects in the Palermo area. A macroseismic survey was carried out soon after the earthquake with the aim of defining, for Civil Protection purposes, the damage scenario over a territory which is densely urbanised. In all, 134 localities were investigated. Damage generally depended on the high vulnerability of the buildings both for problems related to the old age - as is the case of the Palermo historical centre - and for peculiar unfavourable conditions due to site effects, particularly in some quarters of the city and in the nearby locality of Ficarazzi. Damage to masonry consisted of falling plaster, failure of corner walls, diagonal cracks in walls and widening of previous fissures. Some degraded buildings, almost abandoned and with evident lack of maintenance, suffered partial structural failure of roofs and floors. As regards reinforced concrete (RC) frame buildings, several edifices with 5-10 storeys suffered cracks in partitions and infill walls, sometimes with failure of these elements, and falling plaster. Fine cracks in beams of frames have also been observed, but without determining significant structural problems. In general, damage affects the lowest storeys of the RC frame buildings. According to the European Macroseismic Scale 1998, the maximum value of intensity, 6, was assigned to Palermo and Ficarazzi. The earthquake has also provoked effects on natural surroundings. Two types of phenomena have been detected: (i) hydrological effects and (ii) slope instability processes. The most relevant was the landslide which occurred near the village of Cerda, 60 km from the epicentre.
    Description: Published
    Description: 1-15
    Description: 1.11. TTC - Osservazioni e monitoraggio macrosismico del territorio nazionale
    Description: N/A or not JCR
    Description: open
    Keywords: Palermo ; terremoto 2002 ; macrosismica ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 8
    Publication Date: 2021-03-01
    Description: Il presente lavoro è costituito dalla raccolta sistematica delle indagini macrosismiche eseguite in occasione dei terremoti di maggior rilievo verificatisi in Sicilia orientale e Calabria meridionale dal Gennaio 1999 al Gennaio 2001. I rilievi precedenti al Settembre 1999 sono stati effettuati nell’ambito delle attività del Gruppo Nazionale per la Difesa dai Terremoti, svolte presso l’Istituto Internazionale di Vulcanologia – CNR di Catania. Successivamente a tale data le indagini macrosismiche hanno costituito parte integrante delle attività di monitoraggio del Sistema Poseidon. Entrambi gli enti adesso costituiscono la sezione di Catania dell’Istituto Nazionale di Geofisica e Vulcanologia.
    Description: Published
    Description: 1-59
    Description: 1.11. TTC - Osservazioni e monitoraggio macrosismico del territorio nazionale
    Description: N/A or not JCR
    Description: open
    Keywords: Sicilia ; terremoti ; macrosismica ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 9
    Publication Date: 2017-04-04
    Description: After the 1976 Friuli earthquake (Ms = 6.5) in north-eastern Italy that caused about 1,000 casualties and widespread destruction in the Friuli area, the Italian government established the Centro di Ricerche Sismologiche (CRS). This is now a department of the Istituto Nazionale di Oceanografia e di Geofisica Sperimentale (OGS), and it is specifically devoted to the monitoring of the seismicity of north-eastern Italy. Since its inception, the North-East Italy Seismic Network has grown enormously. Currently, it consists of 14 broad-band and 20 short-period seismic stations, all of which are telemetered to and acquired in real time at the OGS-CRS data center in Udine. Data exchange agreements in place with other Italian, Slovenian, Austrian and Swiss seismological institutes lead to a total number of 94 seismic stations acquired in real time, which confirms that the OGS is the reference institute for seismic monitoring of north-eastern Italy. Since 2002, CRS has been using the Antelope software suite as the main tool for collecting, analyzing, archiving and exchanging seismic data. SeisComP is also used as a real-time data exchange server tool. A customized web accessible server is used to manually relocate earthquakes, and automatic procedures have been set-up for moment-tensor determination, shaking-map computation, web publishing of earthquake parametric data, waveform drumplots, state-of-health parameters, and quality checks of the station by spectra analysis. Scripts for email/SMS/fax alerting to public institutions have also been customized. Recently, a real-time seismology website was designed and set-up (http://rts.crs.inogs.it/).
    Description: Istituto Nazionale di Geofisica e Vulcanologia
    Description: Published
    Description: 67-75
    Description: 1.1. TTC - Monitoraggio sismico del territorio nazionale
    Description: JCR Journal
    Description: open
    Keywords: Seismological Research Center ; OGS ; acquiring seismic data ; archiving seismic data ; analyzing seismic data ; exchanging seismic data ; real time ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 10
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    Istituto Nazionale di Geofisica e Vulcanologia
    Publication Date: 2017-04-04
    Description: This is the first volume of an international scientific journal that is dedicated to issues of geoethics and geological culture. Its goal is to inform the Italian and international scientific communities about what emerged at the GeoItalia 2011 conference, attended by not only Italian geoscientists. At this conference, the geoscientists questioned their role in society and the responsibilities that they have to assume as scholars of the planet Earth and experts of the territory. They highlighted the need for rediscovery of the cultural values of geology as a science that can contribute to the construction of correct social knowledge, and the need to be aware that geoethics cannot exist without a real awareness among geoscientists of the cultural value of the Earth sciences.
    Description: Published
    Description: 331
    Description: 5.9. Formazione e informazione
    Description: JCR Journal
    Description: open
    Keywords: Geoethics ; Geoetica ; Geological Culture ; Earth Sciences ; Philosophy ; Education ; 05. General::05.03. Educational, History of Science, Public Issues::05.03.99. General or miscellaneous ; 05. General::05.09. Miscellaneous::05.09.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 11
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    Istituto Nazionale di Geofisica e Vulcanologia
    Publication Date: 2017-04-04
    Description: Prof. Giulio Giorello is amongst the most prominent philosophers of science in Italy and in the world. He is currently Professor of the Philosophy of Science at the University of Milan, Director of the Series ‘Science and Ideas’ (Raffaele Cortina Books Editor), and Literary Journalist of the cultural pages of the Corriere della Sera, one of the most important of the Italian newspapers. In this keynote presentation, in interview form, he talks about the value that the Earth sciences have had through history, framing this group of disciplines in ethical and epistemological terms, and highlighting some important elements that have to be considered in geological activities.
    Description: Published
    Description: 343-346
    Description: 5.9. Formazione e informazione
    Description: JCR Journal
    Description: open
    Keywords: Geoethics ; Geological Culture ; Geoetica ; Giulio Giorello ; Earth Sciences ; Interview ; Philosophy ; Epistemology ; 05. General::05.03. Educational, History of Science, Public Issues::05.03.99. General or miscellaneous ; 05. General::05.09. Miscellaneous::05.09.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 12
    Publication Date: 2020-02-24
    Description: After an earthquake, rapid, real-time assessment of hazards such as ground shaking and tsunami potential is important for early warning and emergency response. Tsunami potential depends on seafloor displacement, which is related to the length, L, width, W, mean slip, D, and depth, z, of earthquake rupture. Currently, the primary discriminant for tsunami potential is the centroid-moment tensor magnitude, MCMT, representing the seismic potency LWD, and w estimated through an indirect, inversion procedure. The obtained MCMT and the implied LWD w value vary with the depth of faulting, assumed earth model and other factors, and is only available 30 min or more after an earthquake. The use of more direct procedures for hazard assessment, when available, could avoid these problems and aid in effective early warning. Here we present a direct procedure for rapid assessment of earthquake tsunami potential using two, simple measures on P-wave seismograms—the dominant period on the velocity records, Td, and the likelihood that the high-frequency, apparent rupture-duration, T0, exceeds 50–55 s. T0 can be related to the critical parameters L and z, while Td may be related to W, D or z. For a set of recent, large earthquakes, we show that the period-duration product T T gives more information on tsunami impact and size than MCMT and other currently used d0w discriminants. All discriminants have difficulty in assessing the tsunami potential for oceanic strike-slip and backarc or upper plate, intraplate earthquake types. Our analysis and results suggest that tsunami potential is not directly related to the potency LWD from the ‘seismic’ faulting model, as is assumed with the use of the MCMT discriminant. Instead, knowledge of w rupture length, L, and depth, z, alone can constrain well the tsunami potential of an earthquake, with explicit determination of fault width, W, and slip, D, being of secondary importance. With available real-time seismogram data, rapid calculation of the direct, period-duration discriminant can be completed within 6–10 min after an earthquake occurs and thus can aid in effective and reliable tsunami early warning.
    Description: Published
    Description: 283-291
    Description: JCR Journal
    Description: restricted
    Keywords: earthquake dynamics ; earthquake source observation ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 13
    Publication Date: 2017-04-04
    Description: Paper introducing and describing the EGU2010 SM1.3 session, "Seismic Centers Data Acquisition" (http://meetingorganizer.copernicus.org/EGU2010/session/2427)
    Description: Session «SM1.3 – Seismic Centers Data Acquisition» at the General Assembly 2010 of the European Geosciences Union (EGU), taking place in Vienna (Austria) between 2–7 May 2010, was organized to present both differences and similarities in operations by different types of seismic data centers in order to share experiences and stimulate constructive discussions. Only a few, widely used, "all-in-one" data acquisition and processing packages are available for seismic data centers, two public domain tools (SeisComP and EarthWorm) and one commercial tool (Antelope). The choice for any particular tool may depend on many different criteria, from operational aspects to scientific results, or on the availability of specific requirements in relation to a specific mission. The development of EarthWorm originally started in 1993 in the USA to replace aging and vendor tied regional processing systems. Antelope, on the other hand, started around 1996 with the aim to have real-time data flow from the field sensors to the scientist. SeisComP also started in the nineties as real-time data acquisition and processing system and evolved initially towards an early warning system for seismic observatories. Protocols have been established to exchange real-time waveform data between the different packages.
    Description: Istituto Nazionale di Geofisica e Vulcanologia
    Description: Published
    Description: 1-7
    Description: 1.1. TTC - Monitoraggio sismico del territorio nazionale
    Description: JCR Journal
    Description: open
    Keywords: EGU2010 ; Seismic Centers ; Data Acquisition ; Antelope ; SeisComP ; EarthWorm ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 14
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    Istituto Nazionale di Geofisica e Vulcanologia
    Publication Date: 2017-04-04
    Description: The international debate in the field of geoethics focuses on some of the most important environmental emergencies, while highlighting the great responsibilities of geoscientists, whatever field they work in, and the important social, cultural and economic repercussions that their choices can have on society. The GeoItalia 2009 and 2011 conferences that were held in Rimini and Turin, respectively, and were organized by the Italian Federation of Earth Science, were two important moments for the promotion of geoethics in Italy. They were devoted to the highlighting of how, and with what tools and contents, can the geosciences contribute to the cultural renewal of society. They also covered the active roles of geoscientists in the dissemination of scientific information, contributing in this way to the correct construction of social knowledge. Geology is culture, and as such it can help to dispel misconceptions and cultural stereotypes that concern natural phenomena, disasters, resources, and land management. Geological culture consists of methods, goals, values, history, ways of thinking about nature, and specific sensitivity for approaching problems and their solutions. So geology has to fix referenced values, as indispensable prerequisites for geoethics. Together, geological culture and geoethics can strengthen the bond that joins people to their territory, and can help to find solutions and answers to some important challenges in the coming years regarding natural risks, resources, and climate change. Starting from these considerations, we stress the importance of establishing an ethical criterion for Earth scientists, to focus attention on the issue of the responsibility of geoscientists, and the need to more clearly define their scientific identity and the value of their specificities.
    Description: Published
    Description: 335-341
    Description: 5.9. Formazione e informazione
    Description: JCR Journal
    Description: open
    Keywords: Geoethics ; Education ; History of science ; Public issues ; General (Philosophy of Earth sciences) ; 04. Solid Earth::04.04. Geology::04.04.99. General or miscellaneous ; 05. General::05.03. Educational, History of Science, Public Issues::05.03.99. General or miscellaneous ; 05. General::05.09. Miscellaneous::05.09.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 15
    Publication Date: 2017-04-04
    Description: A seguito dei tre eventi sismici di magnitudo ≥ 4.0, che tra il 10 e il 12 gennaio 2010 hanno colpito la zona del Fermano-Maceratese (Italia centrale), sono state installate due stazioni della rete sismica temporanea dell’INGV ad integrazione delle reti permanenti, nazionale e regionale, già presenti nell’area.
Questa zona ha una sismicità particolare confinata in uno strato sismogenetico fragile ad una profondità compresa tra 15 e 25 km meritevole di un’analisi dettagliata. Le stazioni sono state collegate in tempo reale al centro di acquisizione della Rete Sismica Nazionale dell’INGV utilizzando dei router UMTS. Questa soluzione si è rivelata estremamente rapida e conveniente. Solo una delle stazioni ha infatti risentito della debolezza del segnale UMTS, ma in generale i dati raccolti hanno contribuito a migliorare le localizzazioni ipocentrali prodotte in tempo reale presso la sala di sorveglianza sismica di Roma. L’integrazione dei dati acquisiti dalle stazioni temporanee ai dati prodotti dalle reti permanenti, ha fornito un dataset di buona qualità già rielaborato per degli studi di dettaglio dell’area.
    Description: Published
    Description: 1-30
    Description: 1.1. TTC - Monitoraggio sismico del territorio nazionale
    Description: N/A or not JCR
    Description: open
    Keywords: Emergency ; Seismic Monitoring ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring ; 04. Solid Earth::04.06. Seismology::04.06.10. Instruments and techniques
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 16
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    Istituto Nazionale di Geofisica e Vulcanologia
    Publication Date: 2017-04-04
    Description: Franco Ferrarotti, Professor emeritus at ‘La Sapienza’ University of Rome; since winning the first Chair in this discipline in Italy in 1961, he has been considered the Father of Italian Sociology. An independent Member of Italian Parliament in the third government (1958-1963), a member of the New York Academy of Sciences, and a ‘visiting Professor’ at many universities in Europe, North America, Russia, Japan and Latin America. Franco Ferrarotti has taught and still teaches in Europe and America, and he has received many awards throughout his career. In this interview, he talks about the social aspects and consequences of Earth sciences studies.
    Description: Published
    Description: 347-348
    Description: 5.9. Formazione e informazione
    Description: JCR Journal
    Description: open
    Keywords: Geoethics ; Geological Culture ; Geoetica ; Social aspects ; Geologists activity ; Scientific information ; Society ; 05. General::05.03. Educational, History of Science, Public Issues::05.03.99. General or miscellaneous ; 05. General::05.09. Miscellaneous::05.09.99. General or miscellaneous
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  • 17
    Publication Date: 2017-04-03
    Description: Computing the magnitude of an earthquake requires correcting for the propagation effects from the source to the receivers. This is often accomplished by performing numerical simulations using a suitable Earth model. In this work, the energy magnitude Me is considered and its determination is performed using theoretical spectral amplitude decay functions over teleseismic distances based on the global Earth model AK135Q. Since the high frequency part (above the corner frequency) of the source spectrum has to be considered in computing Me, the influence of propagation and site effects may not be negligible and they could bias the single station Me estimations. Therefore, in this study we assess the inter- and intrastation distributions of errors by considering the Me residuals computed for a large data set of earthquakes recorded at teleseismic distances by seismic stations deployed worldwide. To separate the inter- and intrastation contribution of errors, we apply a maximum likelihood approach to the Me residuals. We show that the interstation errors (describing a sort of site effect for a station) are within ±0.2 magnitude units for most stations and their spatial distribution reflects the expected lateral variation affecting the velocity and attenuation of the Earth's structure in the uppermost layers, not accounted for by the 1-D AK135Q model. The variance of the intrastation error distribution (describing the record-to-record component of variability) is larger than the interstation one (0.240 against 0.159), and the spatial distribution of the errors is not random but shows specific patterns depending on the source-to-station paths. The set of coefficients empirically determined may be used in the future to account for the heterogeneities of the real Earth not considered in the theoretical calculations of the spectral amplitude decay functions used to correct the recorded data for propagation effects.
    Description: Published
    Description: 1444-1454
    Description: JCR Journal
    Description: restricted
    Keywords: time series analysis ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
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  • 18
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    Istituto Nazionale di Geofisica e Vulcanologia
    Publication Date: 2017-04-04
    Description: We argue here that the introduction of an ethical code of conduct that follows the example of the Hippocratic Oath of physicians will help geologists to acquire binding awareness of their professional and social responsibilities. The ethical behavior and obligations of modern geologists involve, but are not limited to, the following issues: correct land/ environment use and management; respect of truth and science; and protection of the Earth systems, on both the local and global scales, and therefore, of our well-being. We believe that for geoligists, the explicit acceptance of an ethical code will help to promote: (i) an awareness of their social role, expertise and sense of belonging to a professional community; (ii) an understanding of the expectations of citizens and society; and (iii) cultural growth, with better use of research and implementation of scientific and professional skills. All this should enhance the public recognition of the social mission of geologists, which is essential for the well-being of society. Therefore, we suggest that like in the majority of medical schools, ethical training should be a part of the university curriculum for students in geology.
    Description: Published
    Description: 365-369
    Description: 5.9. Formazione e informazione
    Description: JCR Journal
    Description: open
    Keywords: Geoethics ; Geological Culture ; Geoetica ; Hippocratic Oath ; Geologists ; Social responsibility ; 05. General::05.03. Educational, History of Science, Public Issues::05.03.99. General or miscellaneous ; 05. General::05.09. Miscellaneous::05.09.99. General or miscellaneous
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  • 19
    Publication Date: 2017-04-04
    Description: The 2009 April 6, Mw= 6.3 L’Aquila earthquake occurred within a complex system of NW–SE trending normal faults in the Abruzzi Central Apennines (Italy). We analyse the coseismic deformation as measured by 〉70 global positioning system (GPS) stations, both from continuous and survey-mode networks, providing unprecedented details for a moderate normal faulting earthquake in Italy from GPS measurements. We use rectangular, uniform-slip, dislocations embedded in an elastic, homogeneous and isotropic half-space and a constrained, non-linear optimization algorithm, to solve for the best-fitting rectangular dislocation geometry and coseismic-slip distribution. We use a bootstrap approach to investigate uncertainties in the model parameters and define confidence bounds for all the inverted parameters. The rupture occurred on a N129°E striking and 50° southwestward dipping normal fault, in agreement with geological observations of surface breaks along the Paganica fault. Our distributed slip model exhibits a zone of relatively higher slip (〉60 cm) between ∼1.5 and ∼11 km depth, along a roughly downdip, NW–SE elongated patch, confined within the fault plane inverted assuming uniform-slip. The highest slip, of the order of ∼1 m, occurred on a ∼16 km2 area located at ∼5 km depth, SE of the mainshock epicentre. The analysis of model resolution suggests that slip at depth below ∼5 km can be resolved only at a spatial scale larger than 2 km, so a finer discretization of different asperities within the main patch of coseismic-slip is not allowed by GPS data. We compute the coseismic Coulomb stress changes in the crustal volume affected by the major aftershocks, and compare the results obtained from the uniform-slip and the heterogeneous-slip models. We find that most of the large aftershocks occurred in areas of Coulomb stress increase of 0.2–13 bar and that a deepening of the slip distribution down to a depth greater than 6 km in the SE part of the fault plane, in agreement with the inverted slip model, can explain the deepest, April 7, Mw 5.3 aftershock.
    Description: Published
    Description: 473-489
    Description: 1.9. Rete GPS nazionale
    Description: 3.2. Tettonica attiva
    Description: JCR Journal
    Description: reserved
    Keywords: Satellite geodesy ; Space geodetic surveys ; Earthquake ground motions ; Earthquake source observations ; Earthquake interaction, forecasting, and prediction ; 04. Solid Earth::04.03. Geodesy::04.03.01. Crustal deformations ; 04. Solid Earth::04.03. Geodesy::04.03.07. Satellite geodesy ; 04. Solid Earth::04.06. Seismology::04.06.01. Earthquake faults: properties and evolution ; 04. Solid Earth::04.06. Seismology::04.06.02. Earthquake interactions and probability ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
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  • 20
    Publication Date: 2021-11-09
    Description: Il 24 maggio 2011, alle 12.40 UTC, la Rete Sismica Nazionale (RSN) dell’Istituto Nazionale di Geofisica e Vulcanologia (INGV) ha registrato un evento sismico di magnitudo (ML) 3.1 nel distretto sismico1 [Selvaggi et al., 1996] del Montefeltro (in provincia di Forlì-Cesena). Nelle successive due settimane sono stati localizzati dalla Sala di Sorveglianza Sismica della sede romana dell’INGV oltre 600 eventi di cui 13 di ML ≥ 3.0. Otto di questi eventi più energetici sono accaduti entro le prime 16 ore dalla prima scossa. L’evento di maggiore energia si è verificato la notte tra il 24 e il 25 maggio (ore 22.03 UTC del 24 maggio) con una magnitudo pari a ML 3.7 (Tabella 1). Considerando la peculiare evoluzione della sequenza nelle prime 24 ore dal primo evento, la prossimità dell'area epicentrale all’Alta Val Tiberina (AVT nel seguito) dove è attualmente in corso un esperimento sismico passivo [Progetto NOVAT2; Cattaneo et al., 2011; D’Alema et al., 2011] e l’apprensione che stava diffondendosi tra la popolazione, è stato ritenuto opportuno attivare le procedure di risposta ad una emergenza sismica e predisporre un intervento volto a migliorare la copertura strumentale dell'area. Il 25 maggio, in accordo con i colleghi INGV della Sezione di Pisa, dell’Osservatorio di Arezzo [Braun, 2006], della sede di Ancona e della Fondazione Prato Ricerche3, si è proceduto con l'istallazione di una rete sismica temporanea ad integrazione delle stazioni permanenti già presenti in zona. Nella giornata del 27 maggio, due delle stazioni temporanee sono state predisposte per la trasmissione in tempo reale alla Sala di Sorveglianza Sismica di Roma dei dati acquisiti, per migliorare la precisione delle localizzazioni prodotte. Nel contempo, sono stati curati dei comunicati informativi divulgati attraverso il sito web4 dell’Ente, parzialmente inclusi in questo lavoro, per dare una risposta alla popolazione interessata dalla sequenza e fortemente preoccupata dall’intensificarsi della sismicità. Il presente lavoro, la cui redazione è stata completata mentre la sequenza è ancora in corso, vuole essenzialmente descrivere le procedure che vengono attivate all’INGV in risposta ad una emergenza sismica e fornire uno strumento tecnico di supporto alla successiva elaborazione della base dati raccolta nel corso dell'esperimento. Viene quindi presentata una breve introduzione sulle conoscenze sismologiche dell’area interessata dalla sequenza, vengono descritti i comunicati emessi dall’INGV per informare i cittadini e viene descritto l’intervento della rete sismica temporanea, ovvero la tempistica dell'istallazione, la strumentazione utilizzata, e i siti occupati.
    Description: Published
    Description: 1-17
    Description: 1.1. TTC - Monitoraggio sismico del territorio nazionale
    Description: N/A or not JCR
    Description: open
    Keywords: Seismic Monitoring ; Emergency ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
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  • 21
    Publication Date: 2017-04-04
    Description: L’uso del rumore ambientale nella valutazione della risposta sismica locale sta diventando molto frequente data la sua facile applicabilità e sensibilità alla variazione spaziale della geologia superficiale. Ciò lo rende particolarmente adatto nelle aree urbane, dove la natura delle unità geologiche affioranti è mascherata dagli interventi antropici. Il lavoro descrive i metodi di acquisizione e di trattamento dei dati, utilizzati durante una campagna svoltasi nell'area urbana di Catania.
    Description: Published
    Description: 1-30
    Description: 1.8. Osservazioni di geofisica ambientale
    Description: N/A or not JCR
    Description: open
    Keywords: NOISE ; ACQUISIZIONE ; URBANA ; CATANIA ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring ; 04. Solid Earth::04.06. Seismology::04.06.10. Instruments and techniques ; 05. General::05.01. Computational geophysics::05.01.01. Data processing
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  • 22
    Publication Date: 2020-11-20
    Description: Il presente lavoro è costituito dalla raccolta sistematica delle indagini macrosismiche eseguite in occasione dei terremoti più energetici verificatisi in Sicilia orientale dal Gennaio 2002 al Dicembre 2005. Esso rappresenta l’estensione, agli anni più recenti, della compilazione effettuata per il periodo 1999-2001 [Azzaro et al., 2002], e più in generale è inserita nel contesto delle attività di pronto intervento macrosismico effettuate regolarmente in ambito regionale dal 1988. L’esecuzione di rilievi in occasione di eventi sismici significativi è una prassi ormai consolidata nelle attività di monitoraggio dell’INGV, che recentemente ha istituito a tal fine il gruppo di lavoro denominato QUEST (QUick Earthquake Survey Team, DP n° 44 del 25/02/2004). I dati raccolti assolvono ad una duplice funzione: 1) nell’immediatezza di un evento sismico, a definire il quadro degli effetti a supporto degli interventi di Protezione Civile e della Comunità Scientifica; 2) a risolvere lacune e problemi interpretativi dei terremoti del passato attraverso il confronto con gli effetti macrosismici degli eventi attuali. La raccolta sistematica di dati macrosismici anche nel caso di eventi di bassa magnitudo, che interessano estensioni areali limitate come quelle etnee, è comunque importante per l’implementazione di banche dati e cataloghi macrosismici sia a livello locale che nazionale. Nel primo caso è stato aggiornato il catalogo macrosismico dei terremoti etnei [Azzaro et al., 2000], recentemente reso disponibile anche su Internet. Nel secondo caso, la più recente versione del catalogo parametrico dei terremoti italiani [Gruppo di Lavoro CPTI, 2004] utilizzata per la redazione della nuova mappa di pericolosità sismica del territorio nazionale (Ordinanza PCM 3274 del 20/03/2003), incorpora i dati dei terremoti siciliani al di sopra della soglia del danno pubblicati in Azzaro et al. [2002, 2003]. I rilievi macrosismici di seguito riportati sono relativi a tutti i terremoti oltre la soglia del danno verificatisi nel periodo considerato, ovvero a quegli eventi che sono stati avvertiti in modo significativo dalla popolazione (Figura 1). In larga parte si tratta di eventi di area etnea che, soprattutto nel corso del 2002, hanno provocato effetti macrosismici di rilievo. Tra i terremoti regionali riportati, non è incluso il terremoto di Palermo del 2002 per il quale è disponibile uno studio specifico [Azzaro et al., 2003].
    Description: Published
    Description: 1-62
    Description: 1.11. TTC - Osservazioni e monitoraggio macrosismico del territorio nazionale
    Description: N/A or not JCR
    Description: open
    Keywords: NONE ; Sicilia ; terremoti ; macrosismica ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring ; 05. General::05.02. Data dissemination::05.02.02. Seismological data
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  • 23
    Publication Date: 2017-04-04
    Description: Red Pompeian paintings, very famous for their deep intensity, are currently suffering from darkening. The origins of this darkening degradation are not clearly identified yet and remain a major issue for curators. In the specific case of cinnabar (HgS)-based red pigment, a photoinduced conversion into black metacinnabar is usually suspected. This work is focused on the blackening of red cinnabar paintings coated on a sparry calcite mortar. Different samples exhibiting different levels of degradation were selected upon visual observations and analyzed by synchrotron-based microanalytical techniques. Atomic and molecular compositions of the different debased regions revealed two possible degradation mechanisms. On one hand, micro X-ray fluorescence elemental maps show peculiar distributions of chlorine and sulfur. On the other hand, X-ray absorption spectroscopy performed at both Cl and S K-edges confirms the presence of characteristic degradation products: (i) Hg- Cl compounds (e.g., corderoite, calomel, and terlinguaite), which may result from the reaction with exogenous NaCl, in gray areas; (ii) gypsum, produced by the calcite sulfation, in black coatings. Metacinnabar is never detected. Finally, a cross section was analyzed to map the in-depth alteration gradient. Reduced and oxidized sulfur distributions reveal that the sulfated black coating consists of a 5-ím-thick layer covering intact cinnabar.
    Description: Published
    Description: 7484-7492
    Description: reserved
    Keywords: Microspectroscopy Analysis ; 05. General::05.09. Miscellaneous::05.09.99. General or miscellaneous
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  • 24
    ISSN: 0894-3230
    Keywords: Menschutkin reaction ; duality of SN1, SN2 mechanisms ; benzyl tosylates ; Yukawa-Tsuno equation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate data for the Menschutkin reaction between strongly activated Z-substituted benzyl p-toluenesulfonates and Y-substituted N,N-dimethylanilines in acetonitrile at 35 °C fit the equation, kobs  =  k1 + k2 [DMA], which is consistent with concurrent first- and second-order processes. The k1 and k2 values for each substrate were separated based on the above equation. The SN1 rate constant, k1, is unaffected by the nature of the nucleophile, whereas the SN2 rate constant, k2, increased with the electron-donating substituent of the N,N-dimethylaniline. The substituent effect on the k1 values is linearly correlated by the Yukawa-Tsuno equation with ρ  =  -5.2 and r  =  1.3. The unimolecular reaction can be regarded as a classical SN1 mechanism. In contrast, that on the k2 values shows an upward curvature when analyzed by the Brown σ+ treatment. These results are ascribed to the simultaneous and independent occurrence of SN1 and SN2 mechanisms in the present Menschutkin reaction. © 1998 John Wiley & Sons, Ltd.
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  • 25
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 231-231 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No Abstract
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  • 26
    ISSN: 0894-3230
    Keywords: calorimetry ; IR spectra ; ketones ; solvation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solution enthalpies of n-hexane, acetone, butan-2-one and octan-2-one in a series of tetrachloromethane-acetonitrile mixtures and the carbonyl stretching absorption frequencies in the IR spectra of these ketones were determined. It was found that over the whole range of concentrations (varying from neat tetrachloromethane up to neat acetonitrile) the solvation enthalpy of these compounds can be obtained additively from the contributions of the alkyl and carbonyl fragments. The solvent effect on the solvation enthalpy of the carbonyl group was found to be satisfactorily correlated with the corresponding IR frequency shifts of the C=O group. It was also found that the sensitivities of the carbonyl IR frequencies to the solvent composition are different for various ketones. From both IR and calorimetric data, the preferential solvation parameters were evaluated. The differences between the IR spectroscopic and calorimetric data are discussed. © 1998 John Wiley & Sons, Ltd.
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  • 27
    Electronic Resource
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    Journal of Physical Organic Chemistry 11 (1998), S. 261-272 
    ISSN: 0894-3230
    Keywords: 1-substituted 2-pyrrolidinones ; C=O stretching frequencies ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an effort to model solute-solvent interactions, the C=O stretching frequencies of five 1-substituted 2-pyrrolidinones and four other carbonyl-containing compounds were measured for 30 common solvents. These were then correlated with four empirical parameter sets and one theoretical (computational) parameter set. While an empirical parameter set gave the best correlation equations, the theoretical parameter equations are physically and statistically significant. Solvent volume, polarizability and hydrogen bond donor acidity (capacity) terms are significant in the correlation equations. © 1998 John Wiley & Sons, Ltd.
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  • 28
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 232-240 
    ISSN: 0894-3230
    Keywords: P - S bond cleavage ; hydroperoxidolysis ; nerve agent VX ; molecular orbital calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The P - S bond cleavage process in the hydroperoxidolysis of a model system for the nerve agent VX was studied using ab initio and semiempirical molecular orbital methods. Aqueous solvation effects were included through single-point calculations using the semiempirical SM5.2PD/A continuum solvation model and geometries optimized at the HF/MIDI! level of theory. The predominant pathway for P - S bond cleavage involves pseudorotation of a low-energy trigonal bipyramidal intermediate followed by apical ligand ejection. In aqueous solution, the free energy barriers for these processes are found to be 14.3 and 4.6 kcal mol-1, respectively, with electronic energies calculated at the MP2/cc-pVDZ//HF/MIDI! level of theory. By comparison with another continuum model of solvation (PCM), it is concluded that the SM5.2PD/A model performs well even for hypervalent phosphorus species, in spite of not having included any such molecules in the model's parameterization set. © 1998 John Wiley & Sons, Ltd.
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  • 29
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 407-410 
    ISSN: 0894-3230
    Keywords: gas-phase thermolysis ; N-methyl-N-phenyl-tert-butylsulfenamide ; morpholinyl-tert-butylsulfenamide ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: N-Methyl-N-phenyl-tert-butylsulfenamide (MPSA) and morpholinyl-tert-butylsulfenamide (MOSA) were thermolyzed in a stirred-flow reactor at temperatures of 340-390 °C and pressures of 7-13 Torr, using toluene as carrier gas, at residence times of 0.3-1.3 s. Isobutene was formed in 99% yield through first-order reactions having the following Arrhenius parameters (A,s-1, Ea, kJ mol-1): MPSA, log A  =  12.41 ± 0.02, Ea  =  158.8 ± 0.2; MOSA, log A  =  12.91 ± 0.22, Ea  =  159 ± 3. It is proposed that the elimination of isobutene takes place by unimolecular reaction mechanisms involving polar, four-center cyclic transition states, forming S-unsubstituted thiohydroxylamines as co-products. Thermochemical parameters, estimated by semiempirical AM1 calculations, are reported for the latter and for the parent molecules. © 1998 John Wiley & Sons, Ltd.
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  • 30
    Electronic Resource
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    Journal of Physical Organic Chemistry 11 (1998), S. 411-418 
    ISSN: 0894-3230
    Keywords: 2,2′-bisbenzimidazolyl ; tautomerism ; NMR ; semi-empirical calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A dynamic NMR study of the tautomerism of 2,2′-bisbenzimidazolyl in DMSO-d6 and a mechanistic interpretation of the process, based on a stepwise, single-proton transfer and formation of a zwitterionic intermediate, are presented. This interpretation is substantiated by semi-empirical calculations of the postulated intermediate and transition state, that yield results which are compared with previous studies on related aliphatic systems. © 1998 John Wiley & Sons, Ltd.
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  • 31
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    Journal of Physical Organic Chemistry 11 (1998), S. 397-406 
    ISSN: 0894-3230
    Keywords: bond dissociation energy ; acidity ; phenylsulfenylamides ; phenylsulfenylanilides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acidities and bond dissociation energies (BDEs) of the N-H bond in two phenylsulfenylamides, PhSNHBz and PhSNH-t-Bu, and four phenylsulfenylanilides, 4-GC6H4NHSPh, where G  =  MeO, H, Br and CN, were measured in order to compare the effects of substituents on acidities and BDEs of N - H bonds with those of C - H bonds. The effects of PhS groups on acidities and BDEs in a series of C - H acids were found to be comparable to those on acidities and BDEs of PhS in a similar series of N - H acids. Comparisons were also made of the effects of changing the oxidation state of sulfur in the series PhS, PhSO and PhSO2 on the acidities and BDEs of adjacent N - H and C - H bonds in weak acids. Hammett-type plots of pKHA values for phenyl benzyl sulfones (4-GC6H4CH2SO2Ph) and phenylsulfenylanilides (4-GC6H4NHSPh) were linear vs σp- values. A linear plot was obtained and explained for a plot of BDE of the N - H bonds in remotely substituted phenylsulfonylanilides with σ+ values. Plots of BDEs vs Eox(A-) were also linear for 4-substituted phenylsulfenylanilides (4-GC6H4NHSPh), phenylsulfonylanilides (4-GC6H4NHSO2Ph) and phenyl benzyl sulfones (4-GC6H4CH2SO2Ph). © 1998 John Wiley & Sons, Ltd.
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  • 32
    Electronic Resource
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    Journal of Physical Organic Chemistry 11 (1998), S. 387-391 
    ISSN: 0894-3230
    Keywords: α-diamides ; 17O NMR ; conformation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 17O NMR spectra of several α-diamides were obtained at natural isotopic abundance in acetonitrile solution in order to study the conformations of these compounds in solution. The 17O NMR shifts vary with the intercarbonyl dihedral angle α in a sense opposite to that observed for α-diketones. © 1998 John Wiley & Sons, Ltd.
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  • 33
    Electronic Resource
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    Journal of Physical Organic Chemistry 11 (1998), S. 392-396 
    ISSN: 0894-3230
    Keywords: 8-azaadenine ; tautomerism ; theoretical study ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The prototropic tautomerism of 8-azaadenine (azaade) was studied theoretically by means of ab initio methods, in both the gas phase and aqueous solution. A number of tautomeric forms were not included in the calculations after applying a stepwise elimination procedure based on both AM1 and HF/6-31G* energy values. The tautomers 9H-azaade, 8H-azaade and 7H-azaade survived to this elimination and their optimized geometries and energies were calculated at the MP2/6-31*//HF/6-31G* level. To include the solvent effects, two self-consistent reaction field method were used: (1) Onsager's SCRF with multipolar expansion up to the hexadecapolar term and (2) the isodensity polarizable continuum method (IPCM). Both methods produce similar results, although the latter represents better the situation in aqueous solution. The stability order in solution, 8H- 〉 9H- 〉 7H-azaade, differs slightly from that found in the gas phase, implying that in general the electrostatic effects in solution are important, but the intrinsic stability of these species in the gas phase overcomes the solvent effect. © 1998 John Wiley & Sons, Ltd.
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  • 34
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    Journal of Physical Organic Chemistry 11 (1998), S. 377-377 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 35
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    Journal of Physical Organic Chemistry 11 (1998), S. 419-425 
    ISSN: 0894-3230
    Keywords: 5-nitro-5′-dimethylamino-2,2′-bisthiophene ; π* probe dye ; cyclic voltammetry ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclic voltamograms of the solvatochromic dye 5-nitro-5′-dimethylamino-2,2′-bisthiophene (1), introduced recently as a sensitive π* probe, were recorded in different solvents. An EPR spectrum of the anionic radical of 1 in DMSO was obtained and compared with other spectra of analogous substituted bisthiophene radicals. It was found that the presence of a donor- acceptor pair of substituents in 1-⋅ reduces significantly the rotational barrier of the radical compared with the unsubstituted bithienyl radical anion 2-⋅. This is the result of an electronic repulsion between the donor ring fragment and the added electron in the coplanar radical, which does not exist in 2-⋅. © 1998 John Wiley & Sons, Ltd.
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  • 36
    ISSN: 0894-3230
    Keywords: calix[4]resorcinarenes ; organophosphorus compounds ; solvatophobic interactions ; host-guest complexation ; high-performance liquid chromatography ; x-ray analysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reversed-phase high-performance liquid chromatography [LiChrosorb RP-18,UV detection at 254 nm and acetonitrile-water (86:14,v/v) as mobile phase] was applied to studies of the host-guest complexation of tetraalkylcalix[4]resorcinareneoctols and their upper rim phosphoryl, sulfonyl and dialkylaminomethyl derivatives with some aromatic guests in the mobile phase. It was shown that the formation of the inclusion complexes results in changes in the retention of aromatic guests and improves their separation. Stability constants of the complexes were calculated from the dependences of the l/k′ values of the aromatic guest on the concentration of the calix[4]resorcinarene in the mobile phase. The molecular structure of 4,6,16,18-tetrahydroxy-10,12,22,24-tetrakis(dipropoxyphosphoryloxy)-2,8,14,20-tetramethylcalix[4]resorcinarene (12) was determined. Crystal data for 12 are P21/n, a  =  16.708(9) Å, b  =  18.683(6) Å, c  =  20.243(5) Å, β  =  95.75(3)°, V  =  6287(4) Å3 and Z  =  4. Compound 12 exists in a boat conformation, in which two opposite unsubstituted resorcinol rings of the macrocyclic skeleton lie in the plane formed by four methine bridges and two diphosphorylated rings are perpendicular to the plane. © 1998 John Wiley & Sons, Ltd.
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  • 37
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    Journal of Physical Organic Chemistry 11 (1998), S. 378-386 
    ISSN: 0894-3230
    Keywords: alkylboronic acids ; arylboronic acids ; ab initio ; MM3 ; molecular mechanics ; force field parameters ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The boronic acid functional group has been incorporated into various biologically important compounds. In order to study this class of compounds better with molecular mechanics, five alkyl- and arylboronic acids were calculated using ab initio methods (Spartan) at the RHF/6-31G* level. MM3 force field parameters were developed based on the theoretically calculated geometries, vibrational spectra, and torsional profiles. © 1998 John Wiley & Sons, Ltd.
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  • 38
    ISSN: 0894-3230
    Keywords: γ-lactones ; base-catalysed hydrolysis ; reactivity-structure correlations ; isobenzofuranones ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate coefficients were measured for the base-catalysed hydrolysis of a series of substituted 3-(phenoxy- or thiophenoxymethylene)-(Z)-1(3H)-isobenzfuranones (3-phenoxy- or thiophenoxymethylenephthalides) in 70% (v/v) aqueous dioxane at 30.0 °C, in addition to the carbonyl stretching frequencies in chloroform and tetrachloromethane following deconvolution and band separation, when required. The Hammett reaction constants for the alkaline hydrolysis of the 3-/4-substituted phenoxy and thiophenoxy series are ca 0.75 and 1.10, respectively. These results are related to electrostatic field and resonance effects. Successful correlations between the carbonyl stretching frequencies and substituent constants and the rates of alkaline hydrolysis were found. Computational studies using the semi-empirical AM1 method correctly model both the details of the mechanistic pathway and the substituent effects. © 1998 John Wiley & Sons, Ltd.
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  • 39
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    Journal of Physical Organic Chemistry 11 (1998), S. 437-447 
    ISSN: 0894-3230
    Keywords: inductive constants ; theoretical estimation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new model of the inductive effect is proposed, allowing highly accurate theoretical calculations of inductive constants for a diversity of substituents, using a simple and readily available system of mathematics. According to this approach, the inductive effect of a substituent is considered in terms of the additive influence of its constituent atoms. A constant inherent capacity for inductive interaction with a reactive center (with a four-coordinate carbon atom chosen for such a center), represented by an atomic constant σA, is ascribed to each atom. Values of σA for a wide variety of atoms are determined, and their physical meaning is revealed to elucidate to a certain extent the physical nature of the inductive effect. In addition, the proposed model permits the convenient use in calculations of group constants σG characterizing the inductive power of groups. Values of σG are determined for molecular fragments that are most widely dealt with in organic chemistry, and the use of σA or σG constants and of their superposition is shown to have, in most cases, little or no effect on the accuracy and reproducibility of the results obtained. It is also shown that, in terms of the developed approach, the inductive effect of a substituent is closely associated with its conformation. Theoretical inductive constants were calculated for 427 organic, aromatic, organometallic and charged substituents, and they showed perfect correlation with the corresponding experimental values. © 1998 John Wiley & Sons, Ltd.
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  • 40
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    Journal of Physical Organic Chemistry 11 (1998), S. 448-454 
    ISSN: 0894-3230
    Keywords: mandelic acid ; alkaline permanganate ; oxidation ; kinetics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the oxidation of mandelic acid (MA) by permanganate in aqueous alkaline medium at a constant ionic strength of 1.0 mol dm-3 were studied spectrophotometrically. The reaction shows first-order kinetics in [permanganate ion] and fractional order dependences in [MA] and [alkali]. Addition of products, manganate and aldehyde have no significant effect on the reaction rate. An increase in ionic strength and a decrease in dielectric constant of the medium increase the rate. The oxidation process in alkaline medium under the conditions employed in the present investigation proceeds first by formation of an alkali permanganate complex, which combines with mandelic acid to form another complex. The latter decomposes slowly followed by a fast reaction between the free radical of mandelic acid and another molecule of permanganate to give products. The reaction constants involved in the mechanism were derived. There is good agreement between the observed and calculated rate constants under different experimental conditions. The reaction was studied at different temperatures and activation parameters were computed with respect to the slow step of the proposed mechanism. © 1998 John Wiley & Sons, Ltd.
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  • 41
    ISSN: 0894-3230
    Keywords: Selective arylation ; exocyclic N-position ; 2-pyrimidylnitrenium ion ; tetrazolo[1,5a]pyrimidine ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photo-reactions of tetrazolo[1,5-a]pyrimidine (1) with benzene (2a) and substituted benzenes (2b-f) in the presence of trifluoroacetic acid (TFA) gave 2-(2-, 3- and 4-substituted anilino)pyrimidines (3-5) together with 2-aminopyridine (6) and biphenyl (7) or diarylmethanes (8b, 8c and 8e). From the effect of heavy-atom solvent on the reactions, it is reasonable to assume that 3-5 are formed via a singlet species, but 6-8 via a triplet species. The intermediacy of 2-pyrimidylnitrenium ion is consistent with the evidence derived by the above effect, by a Hammett plot with ρ = -2.9 and by effects of solvent nucleophilicity and counter-anions. The selective exocyclic N-arylation giving 3-5 is discussed. © 1998 John Wiley & Sons, Ltd.
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  • 42
    ISSN: 0894-3230
    Keywords: 3-methyl-2, 4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol esters ; analgesics ; synthesis ; structure ; conformation ; pharmacological assays ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of esters derived from 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol (1) was synthesized and studied by 1H and 13C NMR spectroscopy, and the crystal structure of 3-methyl-2,4-diphenyl-9α-(3,5-dimethylbenzoyloxy)-3-azabicyclo[3.3.1]nonane (2) was determined by x-ray diffraction. The compounds studied display in CDCl3 a preferred flattened chair-chair conformation. This bicycle conformation is similar to that found for 2 in the crystal state. Pharmacological assays on mice were performed to evaluate drug-induced behavioral alteration, peripheral or central acute toxicity and analgesic activity. © 1998 John Wiley & Sons, Ltd.
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  • 43
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    Journal of Physical Organic Chemistry 11 (1998), S. 101-108 
    ISSN: 0894-3230
    Keywords: encounter complexes ; 1-cyanonaphthalene ; norbornadiene ; stereospecific ; nucleophilic trapping ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photo-induced electron donor-acceptor reactions between 1-cyanonaphthalene (CNN) and norbornadiene (N) generate products of several structure types. Methanol adducts (1-3) formed in polar solvents are rationalized via the radical cation, N+·, and stereospecific (exo-) nucleophilic attack by methanol. In less polar solvents, CNN and N form [2 + 2]-cycloadducts, exclusively on the exo-face of N. In non-polar solvents containing methanol, CNN, N and methanol combine to form 1:1:1 adducts, containing the sensitizer on the endo- and the methoxy groups on the exo-face. The formation of these products is rationalized via the trapping of encounter complexes of different geometries. Any rearrangement of the norbornenyl system can be eliminated, since neither tricyclyl nor 7-methoxynorbornenyl structures are formed. Apparently, the alcohol captures an endo-encounter complex of CNN and N by attack from the exo-face, similar to the attack of methanol on N+·. © 1998 John Wiley & Sons, Ltd.
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  • 44
    ISSN: 0894-3230
    Keywords: aromaticity ; Diels-Alder transition states ; Diels-Alder adducts ; reaction mechanism ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Semiempirical, ab initio and DFT investigations on the mechanism of the Diels-Alder reactions of a set of masked dienes (ring-fused dienes), viz. o-quinodimethane, anthracene and α-vinylnaphthalene, with ethylene, and reactions of α-vinylnaphthalene with maleic anhydride and p-benzoquinone were performed with a view to understanding the role of masking factors on the activation and reaction energies. The reactions were found to occur in a concerted fashion through synchronous transition states (TSs) in the first two reactions and through asynchronous TS in the other case. Of the compounds studied, o-quinodimethane is the most reactive diene both in a kinetic and a thermodynamic sense. α-Vinylnaphthalene reacts faster with maleic anhydride than p-benzoquinone, as expected, and two possible stereoselective TSs, one endo and the other exo, have been located for the reactions of α-vinylnaphthalene with the above dienophiles. Calculations show that the relative gain or loss of aromatic stabilization of the benzonoid ring in the transition state and in the product seems to play a major role in the kinetic and thermodynamic control of these reactions. © 1998 John Wiley & Sons, Ltd.
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  • 45
    ISSN: 0894-3230
    Keywords: methylbenzoic acids ; infrared spectra ; conformation ; Chemistry ; Theoretical, Physical and Computational Chemistry
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared spectra of all isomers of polymethyl-substituted benzoic acids were recorded in the carbonyl and hydroxyl regions in tetrachloromethane at various concentrations and interpreted in terms of conformation. According to a plot of ν(C=O) of the monomeric form vs Hammett substituent constants σ, these compounds may be classified into two classes. Derivatives with none or only one methyl group in the ortho position are concluded to exist in an equilibrium of two planar conformations, unless the equilibrium is degenerate. Derivatives with two ortho-situated methyl groups are concluded to take up one non-planar conformation. These findings are supported by the shape of the hydroxyl and carbonyl bands, which are unsymmetrical in the former class, although they could not be reliably separated into bands pertinent to the individual conformers. This conclusion is at variance with the common interpretation which has invariably ascribed to these and similar ortho derivatives non-planar conformations with a variable torsional angle. © 1998 John Wiley & Sons, Ltd.
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  • 46
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    Journal of Physical Organic Chemistry 11 (1998), S. 149-154 
    ISSN: 0894-3230
    Keywords: P - C bond cleavage ; phosphoranyl radicals ; organophosphonate biodegradation ; ab initio calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Barrier heights for P - C bond homolysis in P-hydroxy-P-methyl-P,P-dioxophosphoranyl and P,P,P-trihydroxy-P-methylphosphoranyl were calculated using well correlated levels of electronic structure theory. The best estimate for the difference in barriers between the two indicates that homolysis is more facile for P,P,P-trihydroxy-P-methylphosphoranyl by roughly 9 kcal mol-1. This result suggests that bacterial pathways leading to P - C bond cleavage in organophosphonate derivatives will preferentially proceed via initial one-electron reduction of substrates rather than oxidation. © 1998 John Wiley & Sons, Ltd.
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  • 47
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    Journal of Physical Organic Chemistry 11 (1998), S. 201-208 
    ISSN: 0894-3230
    Keywords: indolizines ; cycloaddition ; reaction mechanism ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The peculiarities of [8+2] cycloaddition reactions of indolizines with dienophiles are reviewed. Quantum chemical SINDO1, AM1 and ab initio calculations of transition states were performed for [8+2] cycloaddition reactions of indolizine and 6-nitroindolizine with a series of alkenes with donor and acceptor groups. The calculations predict a dipolar cycloaddition mechanism (electrophilic addition and ring closure) for reactions of indolizine and 6-nitroindolizine with nitroethylene. For the reaction of 6-nitroindolizine with N,N-dimethylaminoethylene, the predicted mechanism corresponds to a previously unknown ‘inverse’ dipolar cycloaddition (nucleophilic addition and ring closure). © 1998 John Wiley & Sons, Ltd.
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  • 48
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    Journal of Physical Organic Chemistry 11 (1998), S. 115-124 
    ISSN: 0894-3230
    Keywords: cross-interaction constants ; gas-phase nucleophilic substitution reactions ; PM3 MO ; benzyl chlorides ; phenoxides ; thiophenoxides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas-phase nucleophilic substitution reactions of Y-benzyl chlorides with X-phenoxide and X-thiophenoxide nucleophiles were investigated theoretically using the PM3 semi-empirical MO method. The Leffler-Grunwald rate-equilibrium and Brønsted correlations predict that the degree of bond formation in the transition state (TS) is approximately 45 and 40% on the reaction coordinate for the phenoxides and thiophenoxides, respectively. For a weaker nucleophile, a later TS is obtained with an increased bond making and breaking. The variation of the TS structure with substituents in the nucleophile is thermodynamically controlled and is well correlated by rate-equilibrium relationships. In contrast, the TS variation (a tighter TS) with substituent (for a stronger acceptor Y) in the substrate is dependent only on variations of the intrinsic barrier and so cannot be correlated by such thermodynamically based rate-equilibrium relationships. The gas phase ρX and ρY values are much greater in magnitude than those in solution. A similar gas-phase theoretical cross-interaction constant, ρXY (ca -0.60), is obtained for both phenoxides and thiophenoxides, which is in good agreement with the experimental value (-0.62) for the thiophenoxide reactions in MeOH at 20.0 °C. The oxy and sulfur anion bases lead to a similar TS structure, but a lower reactivity for the former is due to a greater endothermicity of the reaction. A relatively wide range variation of the reaction energies, ΔG°, can be ascribed to the loss of resonance stabilization of anion nucleophiles upon product formation. © 1998 John Wiley & Sons, Ltd.
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  • 49
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    Journal of Physical Organic Chemistry 11 (1998), S. 171-176 
    ISSN: 0894-3230
    Keywords: acetaldehyde ; oxidation ; periodate ; osmium (VIII) catalysis ; ruthenium (III) catalysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Os(VIII) and Ru(III) catalysis of the periodate oxidation of acetaldehyde in aqueous alkaline medium was investigated. The catalytic efficiency is Ru(III)〈Os(VIII). The product of oxidation in both cases is acetate and IO3-. The stoichiometry is the same in both catalyzed reactions, i.e. [IO4-]:[CH3CHO] = 1:1. Probable mechanisms are proposed and discussed. The reaction constants involved in the mechanisms are derived. © 1998 John Wiley & Sons, Ltd.
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  • 50
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    Journal of Physical Organic Chemistry 11 (1998), S. 223-229 
    ISSN: 0894-3230
    Keywords: Solvolysis ; Grunwald-Winstein-type analysis ; Hammett-type analysis ; YxBnCl scale ; 1-aryl-1-phenylmethyl cations ; Mulliken population analysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate constants of solvolysis of α-tert-butyl(2-naphthyl)methyl chloride (1), 9-fluorenyl chloride (2) and a series of monosubstituted benzhydryl chlorides (3) in a wide range of solvents were measured. Grunwald-Winstein-type correlation analysis of log k for 2 and 3 against YBnCl, with or without nucleophilicity N, yielded less satisfactory linear correlations than that against log k(1). A new scale of solvent ionizing power, YxBnCl, for the correlation of solvolytic reactivities of benzylic chlorides with extended charge delocalization based on log k(1) was developed. Application to the mechanistic study suggested the solvolysis of 2 and 4-nitrobenzhydryl chloride were non-limiting. Hammett plots against σ+ constants exhibited more negative ρ values in less nucleophilic solvents. In a benzhydryl chloride containing a strong deactivating substituent, such as 4-nitro, the positive charge delocalizes mainly over the unsubstituted ring in the cationic transition state. The uneven charge distribution was also confirmed by Mulliken population analysis at the level of the RHF/6-31G*//RHF/3-21G(*) basis set for cations. Comparison of the results of correlation analysis using the equation log(k/k0) = mY vs the equation log(k/k0) = mY+hI, and using the equation log(k/k0) = mY+lN vs the equation log(k/k0) = mY+lN+hI indicated the use of YBnCl or YxBnCl could give a better understanding of solvolytic mechanisms than the combinatorial use of YCl and I. © 1998 John Wiley & Sons, Ltd.
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  • 51
    ISSN: 0894-3230
    Keywords: Solvent-solute interactions ; β-carotene ; electronic absorption spectrum ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvent effects on the wavenumber of the maximum of the longest wavelength electronic absorption band of all-trans-β-carotene were determined in 34 solvents. Together with results from previous studies, a data set for 51 solvents, mostly non-hydrogen bond donors, was constructed. This information was analyzed in terms of reaction field models and also showed its value for correlation purposes when used either alone or in combination with standard empirical solvent polarity-polarizability scales. © 1998 John Wiley & Sons, Ltd.
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  • 52
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    Journal of Physical Organic Chemistry 11 (1998), S. 177-184 
    ISSN: 0894-3230
    Keywords: nitro derivatives of phenols ; pyrolysis initiation reactions ; impact sensitivity ; UHF-SCF-AM1 MO method ; activation energy. ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The UHF-SCF-AM1 MO method was applied to the study of two kinds of pyrolysis reactions of six nitro derivatives of phenols (homolysis reaction by rupture of the C - NO2 bond into radicals and isomerization reaction involving phenolic hydrogen transferring to oxygen on the NO2 group). The molecular geometries of reactants, transition states and products were fully optimized. The potential energy curves and activation energies were first obtained. The results show that this category of compounds is more easily initiated via isomerization reactions than by homolysis reactions. The parallel relationship among the Wiberg bond order of the pyrolysis-initiation H - O bond in the molecule of a reactant, the activation energy of the isomerization reaction breaking the H - O bond and impact sensitivity of the reactant gives ‘the principle of the smallest bond order’ (PSBO) powerful support. The sensitizing effect of a phenol group was elucidated based on calculation results. The different influences of OH and NO2 groups on the heat of formation of a molecule are discussed. © 1998 John Wiley & Sons, Ltd.
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  • 53
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    Journal of Physical Organic Chemistry 11 (1998), S. 216-222 
    ISSN: 0894-3230
    Keywords: o-carboxybenzohydroxamic acid ; phthalic anhydride ; phthalic acid ; hydrolysis ; intramolecular acid catalysis ; kinetics ; activation parameters ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Phthalic anhydride was detected spectrophotometrically in the hydrolysis of o-carboxybenzohydroxamic acid (OCBA) in CH3CN-H2O solvent containing 0.03 mol dm-3 HCl. Pseudo-first-order rate constants (k1) for hydrolysis of OCBA are almost independent of the change in CH3CN content from 10 to 80% (v/v) in mixed aqueous solvents. The rate constants k1 are more than 10-fold larger than the corresponding rate constants for hydrolysis of phthalamic acid. These observations are explained in terms of a mechanism slightly different from the mechanism for hydrolysis of phthalamic acid. The activation parameters, ΔH* and ΔS*, are not affected appreciably by an increase in CH3CN content from 10 to 80% in mixed aqueous solvents. © 1998 John Wiley & Sons, Ltd.
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  • 54
    ISSN: 0894-3230
    Keywords: solute-solvent interactions ; solvent-solvent interactions ; binary solvents ; alcohol-water mixtures ; water structure ; solvatochromic indicators ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A preferential solvation model that takes into account the enhancement of the structure of water when small amounts of alcohol are added was applied to solvatochromic data for binary mixtures of water with 2-methylpropan-2-ol, propan-2-ol, ethanol and methanol. Application of the model allows the calculation of the effect of the enhancement of the water structure on solvatochromic solvent properties. It is demonstrated that the enhancement of water structure increases the solvent dipolarity/polarizability and hydrogen-bond donor acidity and decreases the solvent hydrogen-bond acceptor basicity. The effect decreases in the order 2-methylpropan-2-ol-water, propan-2-ol-water, ethanol-water and methanol-water. © 1998 John Wiley & Sons, Ltd.
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  • 55
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    Journal of Physical Organic Chemistry 11 (1998), S. 157-170 
    ISSN: 0894-3230
    Keywords: heterolytic bond dissociation energy ; carbon-carbon σ bonds ; hydrocarbons ; structural dependence ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The coordination of a resonance-stabilized hydrocarbon cation and anion yielded a series of unprecedented hydrocarbons, which are susceptible to thermal heterolytic cleavage of carbon-carbon σ bonds in polar media, generating the original ions under reversible conditions. When the component ions were sufficiently stabilized, some ion pairs were even isolated as solids, thus providing the first examples of hydrocarbon salts. The direct observation of the heterolysis by means of spectroscopy permitted reliable thermodynamic treatments of the observed degree of ionic dissociation. Correlation of the free energy of heterolysis with solvent dielectric constants and parameters of ion stabilities such as pKHA, pKR+ and redox potentials revealed the importance of the thermodynamic stabilities of ions, the degree of solvation and steric congestion in the starting molecule as major controlling factors in the heterolysis. © 1998 John Wiley & Sons, Ltd.
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    Journal of Physical Organic Chemistry 11 (1998), S. 273-276 
    ISSN: 0894-3230
    Keywords: N,N-diphenylcarbamoylpyridinium ion ; solvolysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvolyses of the N,N-diphenylcarbamoylpyridinium ion are subject to specific and/or general base catalysis, which can be eliminated by addition of perchloric acid or increased, especially in fluoroalcohol-containing solvents, by addition of pyridine. The uncatalyzed solvolyses in aqueous methanol and aqueous ethanol involve a weakly nucleophilically assisted (l  =  0.22) heterolysis and the solvolyses in the pure alcohols are anomalously slow. © 1998 John Wiley & Sons, Ltd.
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    Journal of Physical Organic Chemistry 11 (1998), S. 209-215 
    ISSN: 0894-3230
    Keywords: securinine ; cationic micelles ; anionic micelle ; non-ionic micelle ; alkaline hydrolysis ; kinetics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of micelles of cetyltrimethylammonium bromide (CTABr), tetradecyltrimethylammonium bromide (TTABr), sodium dodecyl sulfate (SDS) and polyoxyethylene 10 lauryl ether (C12E10) on the rates of alkaline hydrolysis of securinine were studied at a constant [-OH] (0.05 M). An increase in the total concentrations of CTABr, TTABr, SDS and C12E10 from 0.0 to 0.2 M causes a decrease in the observed pseudo-first-order rate constants (kobs) by factors of ca 2.5, 3, 7 and 4, respectively. The observed data are explained in terms of pseudophase and pseudophase ion-exchange (PIE) models of micelle. The binding constants, KS, of securinine with SDS, C12E10, CTABr and TTABr micelles are 32.4, 14.8, 22.1, and 9.1 M-1, respectively. The magnitudes of the second-order rate constants, kM, for the reactions in the micellar pseudophase are negligible compared with the corresponding rate constant, kW, for the reaction occurring in the aqueous pseudophase for CTABr, TTABr, SDS and C12E10. © 1998 John Wiley & Sons, Ltd.
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    Journal of Physical Organic Chemistry 11 (1998), S. 277-282 
    ISSN: 0894-3230
    Keywords: colloidal CdS-induced photochemical reactions ; photocatalytic reactions ; photooxidation ; 2-methylindole ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2-Methylindole (2-MI) is adsorbed on the surface of colloidal CdS particles with an adsorption intensity of 0.6 × 103 dm3 mol-1. A new emission band at 530 nm is produced by forming an exciplex between excited CdS and 2-MI and the red emission due to CdS is simultaneously quenched. The emission maxima of green bands for different indoles increase in the order indole 〈 tryptophan 〈 2-MI 〈 3-MI and are observed at 508, 520, 530 and 540 nm, respectively. The shift in emission maxima is related to the oxidation potential of these substrates. The irradiation of an aerated reaction mixture containing CdS and 2-MI with visible light induces the oxidation of adsorbed 2-MI by photogenerated holes to produce 2-methyl-3-indolinone and 2-acetamidobenzaldehyde. The latter product is formed due to oxidative C - C bond cleavage of the pyrrole ring. The reactivity of trapped holes towards the adsorbed 2-MI is evidenced by a decrease in the lifetime of the red emission of CdS in the presence of 2-MI. In this reaction the possibility of the participation of singlet oxygen is ruled out. A general mechanism of CdS-induced oxidation of indoles is discussed. © 1998 John Wiley & Sons, Ltd.
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  • 59
    ISSN: 0894-3230
    Keywords: crown dithioether ; conformational analysis ; multicomponent equilibrium ; Chemistry ; Theoretical, Physical and Computational Chemistry
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The solid-state molecular structure and the conformational behaviour in solution of the 12-membered crown dithioether 8-methyl-1,4-dioxa-7,10-dithiacyclododecane-5,12-dione were studied by x-ray crystallography, 1H and 13C NMR spectroscopy and molecular mechanics. The conformational rigidity of some constituent structural fragments allowed a detailed analysis of the structure and distribution of the conformers. A protocol for studies of multiconformational equilibrium was developed by means of the combined use of structure calculations and dynamic NMR measurements. © 1998 John Wiley & Sons, Ltd.
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  • 60
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    Journal of Physical Organic Chemistry 11 (1998), S. 321-333 
    ISSN: 0894-3230
    Keywords: metal-catalyzed carbenoid reactions ; iodonium ylides ; sulfonium ylides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transition metal-catalyzed decomposition of phenyliodonium and diphenylsulfonium ylides was investigated with regard to application in asymmetric carbenoid reactions. Phenyliodonium ylides react in the presence of Rh(II) catalysts with the same selectivity in inter- and intramolecular cyclopropanations as the corresponding diazo compounds, and intramolecular CH insertions proceed with identical enantioselectivities. With diphenylsulfonium ethoxycarbonylmethylide the Cu(I)-catalyzed cyclopropanation of olefins affords trans/cis ratios and asymmetric inductions identical with those of diazo compounds, but with Rh(II) catalysts some small, although significant, selectivity variations occur, which are ascribed to coordination of diphenyl sulfide to one of the coordination sites of the catalyst. © 1998 John Wiley & Sons, Ltd.
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  • 61
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    Journal of Physical Organic Chemistry 11 (1998), S. 299-304 
    ISSN: 0894-3230
    Keywords: molecular architecture ; molecule-based magnets ; biopolymers ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Application of the principles of physical organic chemistry to the construction of molecule-based magnets is discussed. Not only the magnetic structures of conventional magnets but also secondary and tertiary structures of biopolymers are instrumental in the molecular design. © 1998 John Wiley & Sons, Ltd.
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  • 62
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    Journal of Physical Organic Chemistry 11 (1998), S. 350-355 
    ISSN: 0894-3230
    Keywords: 1,3-dipoles ; cumulenes ; infrared spectroscopy ; mass spectrometry ; flash vacuum thermolysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the direct investigation of reactive intermediates it is particularly valuable to use a combination of several spectroscopic techniques. This commentary highlights recent examples, using primarily flash vacuum thermolysis for the generation of the intermediates, and matrix IR spectroscopy in conjunction with gas-phase mass spectrometric methods for their identification. The examples include nitrile imines, nitrile ylides, nitrile sulfides and selenides, dinitrogen sulfide and several novel cumulenes (X=C=C=Y, RN=C=C=C=X). © 1998 John Wiley & Sons, Ltd.
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  • 63
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    Journal of Physical Organic Chemistry 11 (1998), S. 305-320 
    ISSN: 0894-3230
    Keywords: poly(alkylmethyldiallylammonium halides) ; aggregation behavior ; polyelectrolytes ; polysoaps ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrophobically modified polyelectrolytes (polysoaps) are a unique class of water-soluble polymers containing distinct hydrophobic and hydrophilic regions. Above a certain concentration, polysoaps form intramolecular and intermolecular aggregates in aqueous solution. They have attracted much attention not only for their ability to mimic some functions demonstrated by biopolymers but also for their important industrial applications. This review highlights some interesting features of novel non-cross-linked and cross-linked poly(alkylmethyldiallylammonium halides) that have been described in recent years. © 1998 John Wiley & Sons, Ltd.
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  • 64
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    Journal of Physical Organic Chemistry 11 (1998), S. 334-340 
    ISSN: 0894-3230
    Keywords: brain chemistry ; membrane proteins ; molecular neurobiology ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Efforts to developed detailed insights into the structure and function of the molecules of memory, thought and sensory perception - physical organic chemistry on the brain - are described. By combining more conventional chemical tools with a number of techniques adapted from modern biology, it is now possible to perform systematic structure-function studies on the integral membrane proteins that play a central role in molecular neurobiology. There are substantial challenges associated with such studies, but we believe the potential payoff is considerable. © 1998 John Wiley & Sons, Ltd.
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  • 65
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    Journal of Physical Organic Chemistry 11 (1998), S. 341-349 
    ISSN: 0894-3230
    Keywords: vicarious nucleophilic substitution ; hydrogen ; mechanism ; orientation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrogens located at activated positions in electrophilic arenes, e.g. ortho and para hydrogens in nitrobenzenes, can be replaced with a nucleophile moiety provided there is at least one nucleofuge X connected to the nucleophilic centre. As the group really leaving in this hydrogen substitution process is not the hydride anion but X, the reaction has been named vicarious nucleophilic substitution of hydrogen (VNS). The concepts on the mechanism of the reaction and their experimental background are presented. Reactivity and orientation - the fundamental questions concerning synthetical applications of VNS - are discussed in light of the supposed mechanistic picture.
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    Journal of Physical Organic Chemistry 11 (1998), S. 291-291 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 67
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    Journal of Physical Organic Chemistry 11 (1998), S. 362-376 
    ISSN: 0894-3230
    Keywords: highly strained cyclophanes ; reactivity ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An essential feature of the concept of aromaticity has been the stability and lack of reactivity of aromatics relative to that of other unsaturated compounds. Contrary to this general experience, high and unusual reactivity is encountered when simple, monocyclic benzene rings are bent by short bridges into a boat-shaped conformation, as is the case in small [n] paracyclophanes (n ≤ 8) and [n]metacyclophanes (n ≤ 7). This is illustrated, mostly with examples taken from the authors' own work, for thermal and photochemical behavior and reactions with electrophiles, nucleophiles and dienophiles. © 1998 John Wiley & Sons, Ltd.
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  • 68
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    Journal of Physical Organic Chemistry 11 (1998), S. 356-361 
    ISSN: 0894-3230
    Keywords: heterogeneous catalysis ; organic reactions ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A decade's worth of work is reviewed: building on the demonstrated prowess of heterogeneous catalysis in industrial organic chemistry, the author's laboratory devised efficient catalysts for a number of organic reactions, based on aluminosilicates such as clays and zeolites. This review also spells out, at a time when creative research is overshadowed by imitative research, some of the methodological musts that also happen to characterize physical organic chemistry: the devising of experiments so that accurate numerical data can be obtained; the importance of remote, interdisciplinary connections; the need for estrangement from stereotypic preconceptions that may obscure the true explanations for the phenomena; and the over-riding need for concerning oneself only, or at least predominantly, with the important facts that nature tells, if one cares to listen. © 1998 John Wiley & Sons, Ltd.
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  • 69
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    Journal of Physical Organic Chemistry 11 (1998), S. 292-298 
    ISSN: 0894-3230
    Keywords: flash-photolysis ; short-lived reaction intermediates ; mandelic acid ; keto-enol tautomers ; enzyme-catalyzed racemization ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The advantage of adding more structure-diagnostic information to the simple detection of flash photolytically generated transient species by changes in UV-visible light absorbance is illustrated by a case study involving the mandelic acid keto-enol system. An early report based on preliminary evidence proposed that flash photolysis of phenyldiazoacetic acid produces the enol of mandelic acid by hydration of phenylhydroxyketene, itself generated by a photo-Wolff reaction of the diazo acid. Further examination, however, shows that this is only a minor route, and that the major pathway is a new enol-forming reaction involving what appears to be hydration of a carboxycarbene formed by dediazotization of the diazo compound. Hydration of phenylhydroxyketene is nevertheless the reaction by which mandelic acid enol is generated when esters of benzoylformic acid are the flash photolysis substrates. These mechanisms, and also identification of the enol as a tranisent species, are supported by detailed arguments involving acid-base catalysis, solvent isotope effects, and the use of oxygen-18 as a tracer. The work produces a keto-enol equilibrium constant for the mandelic acid system, pKE  =  16.19, and also acidity constants of the enol ionizing as an oxygen acid, pKEa  =  6.39, and the keto isomer ionizing as a carbon acid, pKKa  =  22.57. The bearing of these results on the enzyme-catalyzed racemization of mandelic acid is discussed. © 1998 John Wiley & Sons, Ltd.
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    International Journal of Quantum Chemistry 67 (1998), S. 1-9 
    ISSN: 0020-7608
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new way of analyzing measured or calculated vibrational spectra in terms of internal vibrational modes associated with the internal parameters used to describe geometry and conformation of a molecule is described. The internal modes are determined by solving the Euler-Lagrange equations for molecular fragments φn described by internal parameters ζn. An internal mode is localized in a molecular fragment by describing the rest of the molecule as a collection of massless points that just define molecular geometry. Alternatively, one can consider the new fragment motions as motions that are obtained after relaxing all parts of the vibrating molecule but the fragment under consideration. Because of this property, the internal modes are called adiabatic internal modes, and the associated force constants ka, adiabatic force constants. Minimization of the kinetic energy of the vibrating fragment φn yields the adiabatic mass ma (corresponding to 1/Gnn of Wilson's G matrix) and, by this, adiabatic frequencies ωa. Adiabatic modes are perfectly suited to analyze and understand the vibrational spectra of a molecule in terms of internal parameter modes in the same way as one understands molecular geometry in terms of internal coordinates.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 1-9, 1998
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    International Journal of Quantum Chemistry 67 (1998), S. 133-141 
    ISSN: 0020-7608
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We explore the viability of a time-independent quantum adiabatic switching algorithm in the Fourier grid Hamiltonian (FGH) framework in the presence of degeneracy, avoided crossing, and chaos. The algorithm is simple and cost effective and provides information about the full eigenspectrum of the evolving Hamiltonian. It is shown to be capable of capturing accurately the change in the pattern of level spacing distribution statistics as one switches from a nonchaotic region of parameter values into the chaotic region. The Transition turns out to be less sharp than anticipated.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 133-141, 1998
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    International Journal of Quantum Chemistry 67 (1998), S. 175-185 
    ISSN: 0020-7608
    Keywords: potential dependence ; vibrational frequency ; coinage metal electrodes ; relativistic effects ; density functional calculation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The adsorptive properties of cyanide (CN-) on coinage metal (M) electrodes (M=Cu, Ag, Au) have been investigated using a relativistic density functional method. The way to model the electrochemical potential applied to the electrodes is to consider the systems in the presence of a perturbative external field F. The field-perturbative approach is proven to be a suitable method in interpreting the observed spectral shifts with electrode potential. The calculated potential-dependent shifts of ωM(SINGLE BOND)CN and ωC(SINGLE BOND)M are similar for the three metals, in agreement with experiment observations. The relativistic effects are required to account for the similarity in the frequency shifts of ωM(SINGLE BOND)CN. The calculated vibrational tuning rates dωC(SINGLE BOND)N/dF are 6.61×10-7, 6.61×10-7, and 5.64×10-7 cm-1/(V/cm) for M=Cu, Ag, and Au, respectively. The coupling of the M(SINGLE BOND)CN and C(SINGLE BOND)N internal modes contributes significantly (about 25%) to the size of the frequency shifts ΔωC(SINGLE BOND)N of the ligand. The effect of electric fields on the metal(SINGLE BOND)CN- bonding is also investigated. It is shown that changes in the magnitude of CN- to the metal donation and M(SINGLE BOND)CN bond strength occur under the influence of the electric field.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 175-185, 1998
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  • 73
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    International Journal of Quantum Chemistry 67 (1998), S. 205-219 
    ISSN: 0020-7608
    Keywords: coupled-cluster theory ; electron correlation effects ; molecular orbital choice ; reference determinant choice ; quasi-degenerate states ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The impact of the choice of molecular orbital sets on the results of single-reference-state coupled-cluster (CC) methods was studied for the H4 model. This model offers a straightforward way of taking into account all possible symmetry-adapted orbitals. Moreover, the degree of quasi-degeneracy of its ground state can be varied over a wide range by changing its geometry. The CCD, CCSD, and CCSDT approaches are considered. Surfaces representing the dependence of the energy on the parameters defining the orbitals are obtained. It is documented that for every method there exist alternative orbital sets which allow one to obtain more accurate energies than the standard (HF, BO, and NO) ones. However, for many of the former orbital sets, one obtains relatively large one-body amplitudes or one may encounter problems with solving the CC equations by conventional methods. An interesting variety of orbitals which might be useful for studies of quasi-degenerate states by the CCD method was found.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 205-219, 1998
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    International Journal of Quantum Chemistry 67 (1998), S. 239-250 
    ISSN: 0020-7608
    Keywords: coupled-cluster theory ; electron correlation effects ; molecular orbital choice ; reference determinant choice ; quasi-degenerate states ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Model studies of the impact of the choice of molecular orbital sets on the accuracy of the results of the state-universal coupled-cluster method involving one- and two-body excitations (SU-CCSD) were performed for the H4 model, which offers a straightforward way of representing any symmetry-adapted orbitals as well as the possibility of varying over a wide range the degree of quasi-degeneracy of a state. Energies of the three lowest 1A1 states obtained for 13 sets of standard quantum chemical orbitals as well as for a vast variety of nonstandard orbital sets defined by nodes of a two-dimensional grid are compared. It is shown that there exist nonstandard orbital sets that allow one to obtain more accurate energies than the standard orbital sets. It is also demonstrated that the recently defined [K. Jankowski et al., Int. J. Quantum Chem. 67, 221 (1998)] maximum proximity orbitals (MPO) yield more accurate results than any other of the commonly applied orbital sets. These orbitals are especially effective outside the strong-quasi-degeneracy region.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 239-250, 1998
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    International Journal of Quantum Chemistry 67 (1998), S. 341-341 
    ISSN: 0020-7608
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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    International Journal of Quantum Chemistry 67 (1998), S. 221-237 
    ISSN: 0020-7608
    Keywords: coupled-cluster theory ; electron correlation effects ; molecular orbital choice ; reference determinant choice ; quasi-degenerate states ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The impact of the choice of molecular orbital sets on the results of the valence-universal coupled cluster method involving up to three-body amplitudes (VU-CCSDT) was studied for the H4 model. This model offers a straightforward way of representing all possible symmetry-adapted orbitals. Moreover, the degree of quasi-degeneracy of its lowest 1A1 states can be varied over a wide range by changing its geometry. Calculations were performed both for 13 sets of standard quantum chemical orbitals and for a vast variety of nonstandard orbital sets defined by nodes of a two-dimensional orbital grid. The performance of various standard orbital sets in VU-CCSDT calculations is compared. It is also documented that for every quasi-degeneracy region there exist nonstandard orbital sets which allow one to obtain more accurate VU-CCSDT energies than the standard orbital sets. In an attempt to provide a general interpretation for some of the alternative orbital sets, we defined a set of orbitals which maximize the proximity of the model and target spaces - maximum proximity orbitals (MPO). It is demonstrated that outside the strong quasi-degeneracy region the energies obtained for the VU-CCSDT approach based on the MPOs are more accurate than for the standard orbital sets.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 221-237, 1998
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    International Journal of Quantum Chemistry 67 (1998), S. 273-285 
    ISSN: 0020-7608
    Keywords: Lanczos propagation ; laser-molecule interaction ; Chebyshev propagation ; time-dependent Schrödinger equation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two Lanczos subspace propagation techniques are discussed in this work and compared with the Chebyshev method applied to the original Hamiltonian matrix. Both procedures involve the use of a reduced propagator in the Lanczos subspace to calculate the solution to the time-dependent Schrödinger equation but differ in the way the propagator is evaluated. The LSC (Lanczos subspace Chebyshev) expresses the propagator in terms of Chebyshev polynomials that are functions of the tridiagonal Hamiltonian matrix in the Lanczos space. In contrast, the LSV (Lanczos subspace variational) is implemented by solving the eigenproblem in the Lanczos subspace and then performing a variational expansion of the propagator in the M-dimensional eigenvector space. Although the LSV is the same as the reduced propagator scheme proposed by Park and Light, in the present study the LSV is implemented as a one-step long-time propagator. As a numerical example, the interaction of a molecule with a strong laser pulse is investigated. The Hamiltonian is explicitly time dependent in this case, and thus the stationary formalism is employed in this work to solve the time-dependent Schrödinger equation. Application of either the LSC or LSV yields a wave function in the M-dimensional Lanczos subspace. Nonetheless, the transition amplitudes computed from this wave function are in excellent agreement with those calculated by direct application of the Chebyshev method in the original space used to define the Hamiltonian matrix.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 273-285, 1998
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    International Journal of Quantum Chemistry 67 (1998), S. 299-309 
    ISSN: 0020-7608
    Keywords: space symmetry ; periodic ; Bloch functions ; irreducible representations ; crystalline orbitals ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A computational procedure for generating space-symmetry-adapted Bloch functions (BF) is presented. The case is discussed when BF are built from a basis of local functions (atomic orbitals [AOs]). The method, which is completely general in the sense that it applies to any space group and AOs of any quantum number, is based on the diagonalization of Dirac characters. For its implementation, it does not require as an input character tables or related data, since this information is automatically generated starting from the space group symbol and the AO basis set. Formal aspects of the method, not available in textbooks, are discussed.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 299-309, 1998
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    International Journal of Quantum Chemistry 67 (1998), S. 329-338 
    ISSN: 0020-7608
    Keywords: progesterone ; 5α-progestins ; allopregnanedione ; allopregnanolone ; tetrahydroprogesterone ; electronic structure ; ab initio calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Progesterone (P) yields to 5α-reduced progestins, namely 5α-pregnanedione (DHP), tetrahydroprogesterone (THP), and allopregnanolone (ALLO-P). The geometries and electronic structure of these steroids were assessed by ab initio calculations using the 6-31G* basis set. The parameters measured were bond distances, valence angles, and dihedral angles. Likewise, the following were calculated: total energy; frontier orbitals, i.e., highest occupied molecular orbital (HOMO); lowest unoccupied molecular orbital (LUMO); dipole moment; atomic charges; and electrostatic potentials. The frontier orbitals of P were located at the π-double bond. However, the HOMO of the 5α-progestins was extended into the molecule, while the LUMO was confined at the C20 carbonyl group. The atomic charges, electronic density surfaces and electrostatic potentials showed patterns according to the stereochemical arrangement of the C3 and C20 carbonyl and hydroxyl functional groups. Interestingly, P and THP showed the larger dipole moment and high electronic density at the A-ring because the double bond and the 3α-hydroxy group, respectively. The present results might explain to some extent the metabolism of the studied progestins. Similarly, some physicochemical properties, such as dipole moments and electrostatic potentials, seem related with important biological actions such as uterine contractility and control of gonadotropin secretion.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 329-338, 1998
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    International Journal of Quantum Chemistry 67 (1998), S. 321-328 
    ISSN: 0020-7608
    Keywords: geometrically active atomic states ; shape of atomic states ; molecular formation ; molecular shape ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present a theory of molecular formation according to which the shape of polyhedral or coordination compounds is fixed to a very good approximation by the shape of a particular state (or states) of the central atom, which is activated by spin and spacial coupling of optimal strength between this state, called the geometrically active atomic state (GAAS) and the state of the ligands. For a molecule with a central atom, spacial coupling of optimal strength, means that the shape of the GAAS fixes the position of the ligands according to the maximum overlap principle of the Heitler-London, Slater, and Pauling theory of covalent bonding, whereby much of the energy lowering from the free atom limit is obtained by the maximization of the contribution of the exchange integrals. Hence, a direct causal relationship between the shape of the GAAS and the shape of the molecular state at equilibrium seems to exist. This relationship implies a picture of diabatic connection between the geometrically asymptotic region and the equilibrium region, which is driven by the coupled GAAS and provides the “why” of molecular shape. Since the latter is fixed by the shape of the GAAS (in cases of electronic complexity or of molecular instability it is possible that more than one GAAS contribute simultaneously), prediction of the shape of certain large systems can be made based on the a priori recognition of the corresponding GAAS. The concept of the shape of atomic states defined and computed quantum mechanically from the probability distribution ϱ(cos θ12) of the angle θ12 that the position vectors of two electrons form in the given atomic state. Specifically, it is deduced from the distribution's maxima which provide the most probable values of θ12. As shown previously [Y. Komninos and C. A. Nicolaides, Phys. Rev. A 50, 3782 (1994)], ϱ(cos θ12) is obtainable directly from the state-specific expression for the Coulomb interaction, where the Rk integrals are replaced by Legendre polynomials Pk, multiplied by normalization constants and radial overlaps. The theory is demonstrated by explaining the shape of BeH2, BH2, CH4, SiH4, H2O, H2S, NH3, PH3, SF6, and TiH4 in terms of the shapes of the following GAAS. Be: 2s2p 3P0, B: 2s2p2 4P, C: 2s2p3 5S0, Si: 3s3p3 5S0, O: 2s2p5 3P0, S: 3s23p33d 3P0, N: 2s2p4 4P, P: 3s3p33d 4P0, S: 3s3p33d2 7F0, and Ti: 3d24s4p 5G0.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 321-328, 1998
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  • 81
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    International Journal of Quantum Chemistry 67 (1998), S. 367-376 
    ISSN: 0020-7608
    Keywords: density functional applications ; cyclooctatetraene ; oxepin ; anti-aromaticity ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe by ab initio calculations several rings containing eight π electrons, forced into planarity by altering the balance of strain with fused rings. These include a tricyclic fused-cyclopropano ring derivative of cyclooctatetraene suggested by Ermer to be planar in its ground state, an analogous tricyclic oxepin, and cyclobutano ring-fused cyclooctatetraene previously described experimentally. We verify that cyclopropano ring fusion planarizes rings with eight π electrons; however, by bond alternation and magnetic susceptibility suppression, forming the planar ring leaves the system anti-aromatic.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 367-376, 1998
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  • 82
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    International Journal of Quantum Chemistry 67 (1998), S. 399-409 
    ISSN: 0020-7608
    Keywords: Au ; Pt ; H2 adsorption ; AuPt clusters ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linear and triangular AuPtn cluster reactions with H2 are studied theoretically, using ab initio multiconfiguration self-consistent field (MC-SCF) calculations, followed by extensive multireference configuration interaction (MR-CI) variational and perturbative. Both the linear dimer and the triangular trimers capture the hydrogen molecule by the Pt cluster side and by the Au cluster side. Gold has an electronic effect on the Pt activity, more important than a geometrical one, poisoning the Pt activity to dissociate H2 and lowering the adsorption heats. This effect is stronger in the AuPt dimer, where the H2 capture occurs only at the molecular level, without showing hydrogen bond dissociation. The trimers look more active, relaxing the H(SINGLE BOND)H bond until breakage. No activation barriers are observed in all the cases considered. The hydrogen molecule is not able to cross the clusters due to the large barriers present.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 399-409, 1998
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  • 83
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    International Journal of Quantum Chemistry 68 (1998), S. 253-259 
    ISSN: 0020-7608
    Keywords: H2O dissociation ; ab initio calculations ; hydronium ion ; hydroxil ion ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A reaction mechanism of water dissociation is proposed where solvent effects are accounted for via a minimum stable model that considers the interaction of five water molecules. It is based on the fully self-consistent field (SCF) optimized structures of the reactant, product, and transition state, the calculations being at the Hartree-Fock and configuration interaction level [Møller-Plesset second-order perturbation (MP2) and coupled-cluster single and double excitations (CCSD)]. They were performed with four different basis sets that included polarized and diffuse orbitals. The dissociative mechanism leads to the ionic species OH-+H3O+ as stable products and upon analysis of the energy hypersurface, a transition state is found which yields an activation barrier of 21.2 kcal/mol. This value is in good agreement with the experimentally determined enthalpy for the reaction. The contribution of the aggregation energy is emphasized.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 253-259, 1998
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  • 84
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    International Journal of Quantum Chemistry 68 (1998), S. 285-291 
    ISSN: 0020-7608
    Keywords: tight-binding ; band spectrum ; orbital nonorthogonality ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A one-dimensional one-band model is presented which enables a tight-binding calculation to be performed with full rigor. All the multicenter integrals involved in the calculation of the Hamiltonian matrix elements can be analytically computed in terms of a single parameter: the ratio between the lattice spacing and the extension of the “atomic” wave function. Moreover, the exact expression for the spectrum shows how the usual approximations of limiting the range of interactions and neglecting the nonorthogonality of the basis set degrade the results of the calculations.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 285-291, 1998
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  • 85
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    International Journal of Quantum Chemistry 68 (1998), S. 273-284 
    ISSN: 0020-7608
    Keywords: C40 cluster molecule ; C40H4 cluster molecule ; C40X4 cluster molecule ; PM3 semiempirical molecular orbital method ; structures of geometrical optimization ; ionization potential ; energy gap ; heat of formation ; atomization energy ; vibration frequency ; 1,3,5,7-tetrahaloadamantane molecules ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Herein we demonstrate that the C40 cluster molecule is easily formed to Td symmetry structure and its ground state is 5A2 open shell with four unpaired electrons. These four unpaired electrons are located at the tip points of the Td symmetry structure. This work also indicates that these four unpaired electrons can easily react with a single valence atom, such as hydrogen or halogen atoms, to form a stable carbon hydrogen cluster molecule, C40H4, and carbon halogen cluster molecules, C40X4 (X=F, Cl, Br, I), respectively. The PM3 semiempirical molecular orbital method from Gaussian 94W computer program package was applied very well to these cluster molecules. According to the results in this study, the structures of geometrical optimization, ionization potential, energy gap, heat of formation, atomization energy, vibration frequency, and the remaining data of C40H4 and C40X4 cluster molecules. The above-calculated data prove that these unknown cluster molecules are stable and have a stable capacity similar to 1,3,5,7-tetrahaloadamantane molecules. They can be possibly synthesized experimentally in the near future.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 273-284, 1998
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  • 86
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    International Journal of Quantum Chemistry 68 (1998), S. 261-271 
    ISSN: 0020-7608
    Keywords: SN2 reaction ; reaction path Hamiltonian ; intrinsic reaction coordinate ; reaction path curvature ; ab initio calculation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To obtain essential information on the reaction dynamics for the prototype gas-phase SN2 reaction Cl-+CH3Cl→ClCH3+Cl-, the characteristic features of the potential energy surface in the local region around the reaction path were examined by the reaction path Hamiltonian constructed with high-level ab initio molecular-orbital calculations. After the structures of relevant stationary states and the intrinsic reaction coordinate were determined, the transverse vibrational modes, the corresponding frequencies, and the coupling elements between the pairs of normal modes induced by the reaction coordinate motion were calculated at each point along the intrinsic reaction coordinate. It was found that a quite large reaction path curvature appears in the intrinsic barrier slope near the bottom of each of the pre- and postreaction stable-state complexes. This large curvature was clarified to cause the internal vibrational excitation of the products and the requirement of the vibrational excitation of the reactants for reaction occurrence. The complex recrossings across the transition-state theory dividing surface, previously characterized by Hase et al. [J. Chem. Phys. 96, 8275 (1992)] in which trajectories trapped in the Cl-(DOTTED BOND)CH3Cl complex return to the central barrier region, were demonstrated to be attributed to this large curvature. Furthermore, not only the variational effects but also the reaction path curvature effects on the intermediate recrossings that were also characterized by Hase et al., in which trajectories linger near the central barrier, were found to be negligible.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 261-271, 1998
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  • 87
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    International Journal of Quantum Chemistry 68 (1998), S. 293-304 
    ISSN: 0020-7608
    Keywords: multiconfigurational SCF approach ; electron correlation ; high-symmetric molecules ; fullerene ; group theory ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A symmetry-adapted multiconfiguration self-consistent field (MC SCF) approach aimed at calculations of high-symmetry molecules is proposed. The self-consistency procedure applicable to the molecular terms of any symmetry and multiplicity is developed. It holds the symmetry transformation properties of varied molecular orbitals, thus taking advantage of the relationships within the set of two-electron integrals through molecular invariants. For orbital optimization, a unified coupling operator is constructed on the basis of the pseudosecular method providing for efficient convergence to energy minimum. Based on the group-theory technique, computer codes have been developed for straightforward determination of the invariant expansions for two-electron integrals and configuration interaction (CI) matrix elements. Calculated in this way, the expansion coefficients are presented for the three-electron states that originate from joint t1u and t1g shells of an icosahedral fullerene C60, the case important for the calculations of anion C603- representing the charge state of the fullerene molecule in the superconducting ionic solids K3C60 or Rb3C60. The results of MC SCF calculations for lowest quasi-π-electronic states of C603- are discussed.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 293-304, 1998
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  • 88
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    International Journal of Quantum Chemistry 68 (1998), S. 305-315 
    ISSN: 0020-7608
    Keywords: Boys function ; molecular integrals over Gaussian functions ; computation of Boys function ; error function erf(x) ; electron repulsion integrals ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We propose a new expansion for the Boys function ∫01t2jexp(-r2t2) dt appearing in the calculation of molecular two-electron matrix elements if Gaussian basis sets are employed. This expansion involves a power series involving the terms Ci, j(τ) (r2-R2)i multiplied by exp(-τr2), where τ is an optimized parameter τ∊[0, 1]. The performances of the introduced expansion are discussed and illustrated by some numerical experiments. It appears that the proposed expansion is considerably shorter than the customary Taylor series, which in turn is the special case for τ=0. This is of some importance, particularly for higher j values. Further, the proposed expansion enables a single expression for calculating erf(x) for the whole range of variable x. The recursive relations for the expansion coefficients are derived and the truncation errors are estimated. A new method for calculating the Boys function by means of asymptotic series is represented too.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 305-315, 1998
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  • 89
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    International Journal of Quantum Chemistry 68 (1998), S. 357-384 
    ISSN: 0020-7608
    Keywords: completeness ; Gaussian ; orbital ; geminal ; basis set ; Sobolev ; axial symmetry ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Completeness theorems for Gaussian orbital and geminal basis sets of axial symmetry are proved in the space L2 of square integrable functions and in the first and second Sobolev spaces H1 and H2.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 357-384, 1998
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  • 90
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    International Journal of Quantum Chemistry 69 (1998), S. 201-208 
    ISSN: 0020-7608
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ab initio Hartree-Fock crystal-orbital calculations on three ideal fullerite C60 crystals doped with strontium (C60SrN, where N=2, 3, 6) are reported. C60Sr3 is calculated here to be a semiconductor; C60Sr2, a zero-gap semiconductor, and C60Sr6, a one-dimensional metal. The C60SrN are found to be highly ionic as well: The total charge transfers are 3.444, 4.956, and 9.228 e for N=2, 3, and 6, respectively. The possible mechanisms of the observed superconductivity in C60Sr6 are discussed.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 201-208, 1998
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  • 91
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    International Journal of Quantum Chemistry 67 (1998), S. 311-320 
    ISSN: 0020-7608
    Keywords: space symmetry ; periodic ; Bloch functions ; irreducible representations ; crystalline orbitals ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of symmetry-adapted crystalline orbitals (SACOs) in self-consistent-field (SCF) schemes for infinite periodic systems is discussed and documented with reference to many examples. The symmetry information generated during the SACOs construction is used to illustrate some particular features of the computational procedure at special points in the brillouin zone (BZ). An example is also given for the description in terms of irreducible representations of the beryllium band structure. It is shown that the exploitation of point symmetry reduces the cost of the SCF process by more than one order of magnitude in systems with a large number of atoms per unit cell and high number of point symmetry operators.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 311-320, 1998
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  • 92
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    International Journal of Quantum Chemistry 67 (1998), S. 287-297 
    ISSN: 0020-7608
    Keywords: valence bond theory ; symmetric group approach ; paired-permanent-determinant ; ab initio ; nonorthogonal ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new algorithm for nonorthogonal valence bond (VB) method is presented by using symmetric group approach. In the present algorithm, a new function, called paired-permanent-determinant (PPD), is defined, which is an algebrant and has the same symmetry of a corresponding VB structure. The evaluation of a PPD is carried out by using a recursion formula similar to the Laplace expansion method for determinants. An overlap matrix element in the spin-free VB method may be obtained by evaluating a corresponding PPD, while the Hamiltonian matrix element is expressed in terms of the products of electronic integrals and sub-PPDs. In the present work, some important properties of PPDs are discussed, and the primary procedure for the evaluation of PPD is deduced. Furthermore, the expressions for evaluating both the overlap and Hamiltonian matrix elements are also given in details, which are essential to develop an efficient algorithm for nonorthogonal VB calculations. In the present study, some further effective technical considerations will be adopted, and a new ab initio VB program will be introduced.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 67: 287-297, 1998
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  • 93
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    International Journal of Quantum Chemistry 68 (1998), S. 329-350 
    ISSN: 0020-7608
    Keywords: HeH- ; comparative study of errors ; SCF ; electron correlation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Basis set truncation error (BSTE), size extensivity Error (SEE), zero point vibrational energy (ZPVE), and basis set superposition error (BSSE) of HeH- weak van der Waals interaction energy were determined and compared at the self-consistent field (SCF), many-body perturbation theory (MBPT), and coupled cluster (CC) methods using even-tempered functions. Isotope substitution effects and the role of bond function augmentation were taken into account. Apart from core correlation energy error (CCEE), which is absent from HeH- interaction energy, the results confirm that BSTE is the most important source of error, followed by SEE of the truncated configuration interaction (CI) expansion, ZPVE and BSSE in a descending order. Introducing quadrable excitations to the truncated CI expansion reduces the magnitude of SEE by ∼45.7%, and BSSE correction is not necessary even at the electron correlation level. While bond function augmentation reduces BSSE at the Hartree-Fock, it has an oscillating behavior at the electron correlation level.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 329-350, 1998
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  • 94
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    International Journal of Quantum Chemistry 68 (1998), S. 405-413 
    ISSN: 0020-7608
    Keywords: S-states of two electron atoms ; correlated basis function ; factored wave functions ; one- and two-body densities ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple and accurate variational wave function in which the dependence in the interelectronic distance is factored is proposed to describe S-type states of two-electron atomic systems. We introduce a parameterization which generalizes the previous ones used in this same framework and which allows us to obtain in a simple way the wave function of both symmetric and antisymmetric excited states. We performed a systematic analysis of some exact properties such as the virial theorem and the cusp conditions and a study of both the one- and two-body densities. Finally, a comparison among the different correlation functions for these states was performed for helium.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 405-413, 1998
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  • 95
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    International Journal of Quantum Chemistry 68 (1998), S. 415-419 
    ISSN: 0020-7608
    Keywords: LiBeH3-y ; band structure ; hydrogen vacancy ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the present work, the band structure calculations on LiBeH3-y were carried out by employing the tight-binding method based on the extended Hückel molecular orbital (EHMO) approach, and the effect of hydrogen vacancies on the electronic structure of the system was studied. For LiBeH3 without hydrogen vacancies, its band structure has an energy gap of about 2.5 eV near the Fermi level, which reveals that it is a semiconductor or an insulator. If hydrogen vacancies are involved in the system, they result in a downward displacement of the band structure of LiBeH3-y and cause its total density of states at the Fermi level to be increased. In this case, there is no energy gap near the Fermi level and the total density of states for LiBeH3-y bears a strong resemblance to that for a high-temperature superconductor, which implies that LiBeH3-y is similar to a high-temperature superconductor in physical property.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 415-419, 1998
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  • 96
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    International Journal of Quantum Chemistry 69 (1998), S. 1-1 
    ISSN: 0020-7608
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
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  • 97
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    International Journal of Quantum Chemistry 68 (1998), S. 421-429 
    ISSN: 0020-7608
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ab initio Hartree-Fock crystal orbital quantum chemical calculations on various structural models of three-dimensional crystals of trans-polyacetylene and polythiophene were carried out. The results provide insight into the actual structure and symmetry of the crystalline polymers under study, which are not easily amenable to experimental determination. Both conducting polymers under study were calculated to form crystals with monoclinic unit cells. A possible molecular basis of the specific electronic properties of these polymers is discussed.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 68: 421-429, 1998
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  • 98
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    International Journal of Quantum Chemistry 69 (1998), S. 11-19 
    ISSN: 0020-7608
    Keywords: ab initio excitation energy ; five-coordinate vanadate ; ribonuclease active site ; effective fragment potential ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Knowledge of the ionicity of the phosphorane intermediate is important to the analysis of the microscopic mechanism of the hydrolysis of the phosphate ester bond by ribonuclease A (RNase A). Five-coordinate uridine vanadate, an analog of the phosphorane, binds to RNase A as the monoanion. The absorption spectra of the vanadate is a probe of the electronic structure of the active site. An in vacuo theoretical model of H4VO5- is calculated to have transitions only in the far ultraviolet (UV). However, H2VO5C2H4- has one in the near UV as well as others further into the UV. The transition energy of the monoanion calculated in the field of the protein active site with effective fragment potentials shifts modestly to the red. Broad monoanion absorptions are predicted which would overlap an observed incomplete very broad absorption attributed to the complex of uridine vanadate with RNase A. The absorption bands of neutral ethylene glycol vanadate are predicted to be further to the red but also overlap the experimental absorption.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 11-19, 1998
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  • 99
    ISSN: 0020-7608
    Keywords: pharmacophore ; DISCO ; conformational analysis ; antiarrhythmic agents ; dofetilide ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Blockade of cardiac-delayed rectifier potassium current (IKr) is an important mechanism for Class III antiarrhythmic effect. We developed pharmacophores for IKr inhibitors starting from structures of known blockers. To obtain the pharmacophores, DISCO module of SYBYL was used. Conformations required for DISCO computations were provided by Multisearch type conformational analyses. A common five-point three-dimensional relationship was identified for the most active compounds, whereas a four-point pharmacophore forming a subset of the former one, could be developed for less potent agents.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 21-30, 1998
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  • 100
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    International Journal of Quantum Chemistry 69 (1998), S. 3-10 
    ISSN: 0020-7608
    Keywords: neuron ; Hilbert space ; quantum computer ; computational modeling ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A computational model of charge transfer through an associated polyenic system is presented. This model is based on proposed transient alignment of adjacent ethylenes of phospholipid diacyls in the neural membrane. Influx of anions and cations into the cytosol at ∼108 ions/s at ligand-gated channels hypothetically establishes the conditions for charge transfer through adjacent diacyl ethylenes. It is suggested that this process produces interactions between phospholipid potential energy hypersurfaces. These interactions operating in many-dimensional (Hilbert) space represent a form of massively parallel computation. Basic theoretical principles of quantum computing relevant to the present model are briefly discussed. A preliminary computational model of charge transfer through stacked ethylenes is then presented. In this model molecules were aligned with planes parallel and perpendicular. Singly charged counterions were positioned at the ends of the stacks and ab initio Hartree-Fock calculations at the 6-31+G(d, p) level were carried out. Degree of charge transfer between counterions was monitored by Mulliken population analysis from which atomic charges and dipole moments were calculated. The results of these calculations are interpreted in a larger neurobiological context. Models are proposed which relate the charge-transfer process to ion channel dynamics (open/closed), changes in membrane potential, and macroscopic memory systems. A hypothetical feedback circuitry which could regulate membrane potential and prevent recurrent excitation or hyperpolarization is described. Potential tests of the model utilizing photoinduced charge transfer through a polyenic molecular wire are proposed. It is concluded that this research could lead to a better understanding of computational processes in neurophysiology and cognition.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 3-10, 1998
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