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  • Computational Chemistry and Molecular Modeling  (2.365)
  • 04.01. Earth Interior
  • 2020-2023  (11)
  • 1990-1994  (2.365)
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  • 1
    Publikationsdatum: 2022-03-07
    Beschreibung: The investigation of the role played by CO2 circulating within the mantle during partial melting and metasomatic/refertilization processes, together with a re-consideration of its storage capability and re-cycling in the lithospheric mantle, is crucial to unravel the Earth's main geodynamic processes. In this study, the combination of petrology, CO2 content trapped in bulk rock- and mineral-hosted fluid inclusions (FI), and 3D textural and volumetric characterization of intra- and inter-granular microstructures was used to investigate the extent and modality of CO2 storage in depleted and fertile (or refertilized) Sub-Continental Lithospheric Mantle (SCLM) beneath northern Victoria Land (NVL, Antarctica). Prior to xenoliths entrainment by the host basalt, the Antarctic SCLM may have stored 0.2 vol% melt and 1.1 vol% fluids, mostly as FI trails inside mineral phases but also as inter-granular fluids. The amount of CO2 stored in FI varies from 0.1 μg(CO2)/g(sample) in olivine from the anhydrous mantle xenoliths at Greene Point and Handler Ridge, up to 187.3 μg/g in orthopyroxene from the highly metasomatized amphibole-bearing lherzolites at Baker Rocks, while the corresponding bulk CO2 contents range from 0.3 to 57.2 μg/g. Irrespective of the lithology, CO2 partitioning is favoured in orthopyroxene and clinopyroxene-hosted FI (olivine: orthopyroxene = 0.10 ± 0.06 to 0.26 ± 0.09; olivine: clinopyroxene = 0.10 ± 0.05 to 0.27 ± 0.14). The H2O/(H2O + CO2) molar ratios obtained by comparing the CO2 contents of FI to the H2O amount retained in pyroxene lattices vary between 0.72 ± 0.17 and 0.97 ± 0.03, which is well comparable with the values measured in olivine-hosted melt inclusions from Antarctic primary lavas and assumed as representative of the partition of volatiles at the local mantle conditions. From the relationships between mineral chemistry, thermo-, oxybarometric results and CO2 contents in mantle xenoliths, we speculate that relicts of CO2-depleted mantle are present at Greene Point, representing memory of a CO2-poor tholeiitic refertilization related to the development of the Jurassic Ferrar large magmatic event. On the other hand, a massive mobilization of CO2 took place before the (melt-related) formation of amphibole veins during the alkaline metasomatic event associated with the Cenozoic rift-related magmatism, in response to the storage and recycling of CO2-bearing materials into the Antarctica mantle likely induced by the prolonged Ross subduction.
    Beschreibung: Published
    Beschreibung: 106643
    Beschreibung: 2V. Struttura e sistema di alimentazione dei vulcani
    Beschreibung: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Beschreibung: 4V. Processi pre-eruttivi
    Beschreibung: 2TR. Ricostruzione e modellazione della struttura crostale
    Beschreibung: JCR Journal
    Schlagwort(e): CO2 storage ; Sub-Continental Lithospheric Mantle ; Alkaline metasomatism ; Fluid inclusions ; Synchrotron X-ray microtomography ; Inter-granular fluids ; 04.01. Earth Interior ; 04.08. Volcanology
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Publikationsdatum: 2022-04-26
    Beschreibung: Constraining the magmatic 3He/4He signature of fluids degassed from a magmatic system is crucial for making inferences on its mantle source. This is especially important in arc volcanism, where variations in the composition of the wedge potentially induced by slab sediment fluids must be distinguished from the effects of magma differentiation, degassing, and crustal contamination. The study of fluid inclusions (FIs) trapped in minerals of volcanic rocks is becoming an increasingly used methodology in geochemical studies that integrates the classical study of volcanic and geothermal fluids. Here, we report on the first noble gas (He, Ne, Ar) concentrations and isotopic ratios of FI in olivine (Ol) and pyroxene (Px) crystals separated from eruptive products of the Telica and Baru volcanoes, belonging to the Nicaraguan and Panamanian arc-segments of Central America Volcanic arc (CAVA). FIs from Telica yield air corrected 3He/4He (Rc/Ra) of 7.2–7.4 Ra in Ol and 6.1–7.3 in Px, while those from Baru give 7.1–8.0 Ra in Ol and 4.2–5.8 Ra in Px. After a data quality check and a comparison with previous 3He/4He measurements carried out on the same volcanoes and along CAVA, we constrained a magmatic Rc/Ra signature of 7.5 Ra for Telica and of 8.0 Ra for Baru, both within the MORB range (8 1 Ra). These 3He/4He differences also reflect variations in the respective arc-segments, which cannot be explained by radiogenic 4He addition due to variable crust thickness, as the mantle beneath Nicaragua and Panama is at about 35 and 30 km, respectively. We instead highlight that the lowest 3He/4He signature observed in the Nicaraguan arc segment reflects a contamination of the underlying wedge by slab sediment fluids. Rc/Ra values up to 9.0 Ra are found at Pacaya volcano in Guatemala, where the crust is 45 km thick, while a 3He/4He signature of about 8.0 Ra was measured at Turrialba volcano in Costa Rica, which is similar to that of Baru, and reflects possible influence of slab melting, triggered by a change in subduction conditions and the contemporary subduction of the Galapagos hot-spot track below southern Costa Rica and western Panama.
    Beschreibung: Published
    Beschreibung: 2076-3417
    Beschreibung: 1V. Storia eruttiva
    Beschreibung: 2V. Struttura e sistema di alimentazione dei vulcani
    Beschreibung: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Beschreibung: JCR Journal
    Schlagwort(e): Telica volcano ; Baru volcano ; 3He/4He ; fluid inclusions ; CAVA ; slab fluids ; Isotope Geochemistry ; Noble gases ; 04.08. Volcanology ; 04.01. Earth Interior
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Publikationsdatum: 2022-03-15
    Beschreibung: The origin of magmatic fluids along the East African Rift System (EARS) is a long-lived field of debate in the scientific community. Here, we investigate the chemical composition of the volcanic gas plume and fumaroles at Nyiragongo and Nyamulagira (Democratic Republic of Congo), the only two currently erupting volcanoes set on the Western Branch of the rift. Our results are in line with earlier conceptual models proposing that volcanic gas emissions along the EARS mainly reflect variable contributions of either a Sub-Continental Lithospheric Mantle (SCLM) component or a Depleted Morb Mantle (DMM) component, and deeper fluid. At Nyiragongo and Nyamulagira, our study discards a major contribution of a high 3He/4He mantle plume component in the genesis of volcanic fluids beneath the area. High CO2/3He in fumaroles of both volcanoes is thought to reflect carbonate metasomatism in the lithospheric mantle source. As inferred by previous results obtained on the lava chemistry, this carbonate metasomatism would be more pronounced beneath Nyiragongo. This supports the idea of the presence of distinct metasomes within the lithospheric mantle beneath the Western Branch of the rift.
    Beschreibung: Published
    Beschreibung: 120811
    Beschreibung: 1V. Storia eruttiva
    Beschreibung: 2V. Struttura e sistema di alimentazione dei vulcani
    Beschreibung: 6A. Geochimica per l'ambiente e geologia medica
    Beschreibung: JCR Journal
    Schlagwort(e): East African Rift System ; Volcano ; Gas chemistry ; 04.08. Volcanology ; 04.01. Earth Interior
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 4
    Publikationsdatum: 2021-11-29
    Beschreibung: The geological evolution of the western Mediterranean exhibits complicated interactions between orogenic processes and widespread extensional tectonics. The region is located in a convergent plate margin separating Africa and Europe, and consists of marine basins – the Alboran Sea, the Algerian- Provençal Basin, the Valencia trough, the Ligurian Sea and the Tyrrhenian Sea- which formed as back-arc basins since the Oligocene. In most reconstructions, it has been stressed that back-arc extension led to drifting of continental blocks and to large-scale block rotations. The opening of the Ligurian Sea. is in fact the result of counterclockwise rotation of Corsica and Sardinia. From the point of view of seismicity, the south western Alps and northern part of the Ligurian basin are subject to frequent earthquakes of low to moderate magnitudes. However significantly destructive events are known to have occurred in the past (e.g. 1564 and 1887). Apart from these rare large events, regional studies agree in concluding that the important local microseismicity appears to be poorly focused (e.g., COURBOULEX et alii, 2007) and that, if some tectonic lines are documented onland (COURBOULEX et alii, 2001), the active structures at sea remain unknown. It is therefore an essential prerequisite to gain better insight into the deep seismogenic structures along the North Ligurian margin and even farther offshore, in the identified oceanic domain. The fact that some of these structures can undergo ruptures of Mw~6.5, such as the 1887 event (BAKUN & SCOTTI, 2006), suggests that, at least to some extent, instrumental insufficiencies in the detection and location of microseismicity is a limit to identify active faults that have not experienced large instrumented ruptures to date. The irregular coverage provided by regional seismic networks produces a bias in the recording of local seismicity. Permanent stations are naturally limited to land areas and fail to properly constrain seismicity offshore. Taking into consideration the peculiarities of regional dynamics (low strain rates, rare large events and a regular seismic activity limited to small events with M 〈 3-4), even onshore seismicity is insufficiently covered by permanent networks and requires dense temporary instrumenting by mobile stations. Considering the potential threat of strong offshore earthquakes, it is of first importance to characterize faults that are prone to rupture in order to quantify associated seismic and tsunami hazards. Assuming some weak seismicity exists along these faults and remains undetected by onland networks, some marine stations are necessary to address instrumental remoteness and help delineate active structures. Moreover, since the velocity models used for locations are obtained by inverting seismic data and the reliability of their locations depend, in turn, from the quality of the velocity model used for their hypocentral parameters, the constraints on the seismic path provided by a more dense seismic network may contribute to a more accurate reference model. In this study, we profited from the recent developments in sea bottom seismic instrumentation to deploy OBSs above the zones of the North Ligurian to perform seismic shots and obtain the distribution of seismic velocities with 3D active tomography. We also took the opportunity of the long term (6 months) OBSs reduced array to decrease both the detection threshold and recording distances so as to obtain more complete catalogs and better localisations.
    Beschreibung: Published
    Beschreibung: 789-791
    Beschreibung: 1T. Struttura della Terra
    Beschreibung: N/A or not JCR
    Schlagwort(e): 04.01. Earth Interior ; 04.06. Seismology
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 5
    Publikationsdatum: 2021-11-08
    Beschreibung: The circulation of carbon in Earth’s interior occurs through the formation, migration, and ascent of CO2‐ bearing magmas throughout the convective mantle. Their chemical composition spans from carbonatitic to kimberlitic as a result of either temperature and pressure variations or local redox conditions at which partial melting of carbonated mantle mineral assemblages occurs. Previous experiments that focused on melting relations of synthetic CO2‐bearing mantle assemblages revealed the stability of carbonate‐silicate melts, or transitional melts, that have been generally described to mark the chemical evolution from kimberlitic to carbonatitic melts at mantle conditions. The migration of these melts upward will depend on their rheology as a function of pressure and temperature. In this study, we determined the viscosity of carbonate‐silicate liquids (~18 wt% SiO2 and 22.54 wt% CO2) using the falling‐sphere technique combined with in situ synchrotron X‐ray radiography. We performed six successful experiments at pressures between 2.4 and 5.3 GPa and temperature between 1565 °C and 2155 °C. At these conditions, the viscosity of transitional melts is between 0.02 and 0.08 Pa˙s; that is, about one order of magnitude higher than what was determined for synthetic carbonatitic melts at similar P‐T conditions, likely due to the polymerizing effect of the SiO2 component in the melt.
    Beschreibung: Published
    Beschreibung: 223-236
    Beschreibung: 1T. Struttura della Terra
    Beschreibung: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Schlagwort(e): magma, viscosity, redox, carbonate ; 04.01. Earth Interior
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: book chapter
    Standort Signatur Erwartet Verfügbarkeit
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  • 6
    Publikationsdatum: 2022-02-24
    Beschreibung: Changbai Mountains intraplate volcanism (NE China) developed above the 500 km deep stagnant portion of the Pacific slab in the last 20 Ma. The more recent activity includes a shieldforming stage (2.8–0.3Ma), the Tianchi cone construction stage (1.5–0.01Ma), and a calderaforming stage (0.2Ma-present). Detailed studies on the petrogenesis of the volcanic products between the first two stages and the possible role of geodynamics and local tectonics in controlling the volcanism, however, are lacking. Here, we present structural and whole-rock geochemical and zircon Hf isotopic data on Pleistocene dikes of the Changbai Mountains at the transition from the shield-forming to the Tianchi stage with the aim to constrain their age and the source(s) of their parental magma. The dikes represent the shallower feeding system of monogenetic cones and have a NW-SE strike, which is also the preferred strike of the major fault affecting the area and along which the Changbai Mountains monogenetic scoria cones align. The dikes have a potassic affinity and a trachybasaltic composition. Their zircon U–Pb age is 1.19–1.20Ma (Calabrian). The trachybasalts are enriched in Rb, Ba, Th, U, Nb, Ta, K, Pb, and LREE and slightly depleted in Sr, Zr, Hf, Ti, and HREE with a weak negative Eu/Eu* (δEu 0.96–0.97). Trace elements and isotopic compositions are compatiblewith anOIB-type source with an EMI signature. The calculated (87Sr/86Sr)i ( 0.705165–0.705324), (143Nd/ 144Nd)i ( 0.512552–0.512607, εNd(t) −0.58 to −1.65), and Hf model ages (TDM2) of 1768–1562 Ma suggest that the trachybasaltic dikes were contaminated by a Mesoproterozoic, relatively basic lower crust. The source of the Calabrian trachybasalts consists of asthenospheric melts modified by a subcontinental lithospheric mantle. These melts upwell from depth and stop at the crust-mantle interface where underplating processes favor the assimilation of ancient lower crust material. During the ascent to the surface along deep-seated crustal discontinuities, these magmas weakly differentiate.
    Beschreibung: Published
    Beschreibung: 729905
    Beschreibung: 2V. Struttura e sistema di alimentazione dei vulcani
    Beschreibung: JCR Journal
    Schlagwort(e): Changbaishan ; mantle source ; 04.04. Geology ; 04.01. Earth Interior
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 7
    Publikationsdatum: 2021-11-25
    Beschreibung: This study combines new noble gas data from fluid inclusions in minerals from Sabancaya, Ubinas, and El Misti (CVZ, Peru) and Villarica (South Chile, SVZ) with a revised noble gas compilation in the Andes, to identify systematic along arc variations in helium isotope compositions. We find 3He/4He ratios varying from 8.8 RA (Colombia) to 7.4 RA (Ecuador) within the NVZ, and only as high as 6.4 RA in the CVZ (RA is the atmospheric 3He/4He ratio of 1.39 × 10–6). These distinct isotope compositions cannot be explained by variable radiogenic 4He production via slab fluid transport of U and Th in the mantle wedge, since both NVZ and CVZ share similar slab sediment inputs (Th/La ≈ 0.08–0.13). Instead, the progressively more radiogenic 3He/4He signatures in Ecuador and Peru reflect 4He addition upon magma ascent/storage in the crust, this being especially thick in Peru (〉70 km) and Ecuador (〉50 km) relative to Colombia (∼30–45 km). The intermediate compositions in the North (8.0 RA) and South (7.9 RA) Chile, both high sediment flux margins, mostly reflect a more efficient delivery of radiogenic He in the wedge from the subducted (U-Th-rich) terrigenous sediments. Our results bring strong evidence for the major role played by crustal processes in governing noble gas compositions along continental arcs.
    Beschreibung: Published
    Beschreibung: 45-49
    Beschreibung: 1V. Storia eruttiva
    Beschreibung: 2V. Struttura e sistema di alimentazione dei vulcani
    Beschreibung: 4V. Processi pre-eruttivi
    Beschreibung: JCR Journal
    Schlagwort(e): Noble gases ; Fluid inclusions ; Andean volcanic Arc ; crustal contamination ; 04.08. Volcanology ; 04.01. Earth Interior
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 8
    Publikationsdatum: 2021-12-06
    Beschreibung: The Aleutian Arc is remote and highly active volcanically. Its 4,000 km extent from mainland Alaska to Russia’s Kamchatka peninsula hosts over 140 volcanic centers of which about 50 have erupted in historic times. We present data of volcanic gas samples and gas emission measurements obtained during an expedition to the western-most segment of the arc in September 2015 in order to extend the sparse knowledge on volatile emissions from this remote but volcanically active region. Some of the volcanoes investigated here have not been sampled for gases before this writing. Our data show that all volcanoes host high-temperature magmatic-hydrothermal systems and have gas discharges typical of volcanoes in oceanic arcs. Based on helium isotopes, the western Aleutian Arc segment has minimal volatile contributions from the overriding crust. Volcanic CO2 fluxes from this arc segment are small, compared to the emissions from volcanoes on the Alaska Peninsula and mainland Alaska. The comparatively low CO2 emissions may be related to the lower sediment flux delivered to the trench in this part of the arc.
    Beschreibung: Published
    Beschreibung: 786021
    Beschreibung: 2V. Struttura e sistema di alimentazione dei vulcani
    Beschreibung: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Beschreibung: JCR Journal
    Schlagwort(e): Aleutians ; volcano ; gas ; volatiles ; geochemistry ; 04.08. Volcanology ; 04.01. Earth Interior
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 9
    Publikationsdatum: 2021-12-24
    Beschreibung: This article has been accepted for publication in Geophysical Journal International ©: The Authors 2021. Published by Oxford University Press on behalf of the Royal Astronomical Society. All rights reserved. Uploaded in accordance with the publisher's self-archiving policy.
    Beschreibung: Ambient-noise records from the AlpArray network are used to measure Rayleigh wave phase velocities between more than 150,000 station pairs. From these, azimuthally anisotropic phase-velocity maps are obtained by applying the Eikonal tomography method. Several synthetic tests are shown to study the bias in the Ψ2 anisotropy. There are two main groups of bias, the first one caused by interference between refracted/reflected waves and the appearance of secondary wavefronts that affect the phase travel-time measurements. This bias can be reduced if the amplitude field can be estimated correctly. Another source of error is related to the incomplete reconstruction of the travel-time field that is only sparsely sampled due to the receiver locations. Both types of bias scale with the magnitude of the velocity heterogeneities. Most affected by the spurious Ψ2 anisotropy are areas inside and at the border of low-velocity zones. In the isotropic velocity distribution, most of the bias cancels out if the azimuthal coverage is good. Despite the lack of resolution in many parts of the surveyed area, we identify a number of anisotropic structures that are robust: in the central Alps, we find a layered anisotropic structure, arc-parallel at midcrustal depths and arc-perpendicular in the lower crust. In contrast, in the eastern Alps, the pattern is more consistently E-W oriented which we relate to the eastward extrusion. The northern Alpine forleand exhibits a preferential anisotropic orientation that is similar to SKS observations in the lowermost crust and uppermost mantle.
    Beschreibung: German Science Foundation (SPP-2017, Project Ha 2403/21-1); Swiss National Science Foundation SINERGIA Project CRSII2-154434/1 (Swiss-AlpArray); Progetto Pianeta Dinamico, finanziamento MUR-INGV, Task S2 – 2021
    Beschreibung: Published
    Beschreibung: 151–170
    Beschreibung: 1T. Struttura della Terra
    Beschreibung: JCR Journal
    Schlagwort(e): Seismic anisotropy ; Seismic interferometry ; Seismic tomography ; Wave propagation ; Continental tectonics: compressional ; 04.01. Earth Interior ; 04.06. Seismology
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 10
    Publikationsdatum: 2021-12-14
    Beschreibung: We present results from a joint inversion of new seismic and recently compiled gravity data to constrain the structure of a prominent geophysical anomaly in the European Alps: the Ivrea Geophysical Body (IGB). We investigate the IGB structure along the West-East oriented Val Sesia profile at higher resolution than previous studies. We deployed 10 broadband seismic stations at 5 km spacing for 27 months, producing a new database of ∼1000 high-quality seismic receiver functions (RFs). The compiled gravity data yields 1 gravity point every 1–2 km along the profile. We set up an inversion scheme, in which RFs and gravity anomalies jointly constrain the shape and the physical properties of the IGB. We model the IGB’s top surface as a single density and shear-wave velocity discontinuity, whose geometry is defined by four, spatially variable nodes between far-field constraints. An iterative algorithm was implemented to efficiently explore the model space, directing the search toward better fitting areas. For each new candidate model, we use the velocity-model structures for both ray-tracing and observed-RFs migration, and for computation and migration of synthetic RFs: the two migrated images are then compared via cross-correlation. Similarly, forward gravity modeling for a 2D density distribution is implemented. The joint inversion performance is the product of the seismic and gravity misfits. The inversion results show the IGB protruding at shallow depths with a horizontal width of ∼30 km in the western part of the profile. Its shallowest segment reaches either 3–7 or 1–3 km depth below sea-level. The latter location fits better the outcropping lower crustal rocks at the western edge of the Ivrea-Verbano Zone. A prominent, steep eastward-deepening feature near the middle of the profile, coincident with the Pogallo Fault Zone, is interpreted as inherited crustal thickness variation. The found density and velocity contrasts of the IGB agree with physical properties of the main rock units observed in the field. Finally, by frequency-dependent analysis of RFs, we constrain the sharpness of the shallowest portion of the IGB velocity discontinuity as a vertical gradient of thickness between 0.8 km and 0.4 km.
    Beschreibung: The Swiss National Science Foundation (SNF) supported this research (grant numbers PP00P2_157627 and PP00P2_187199 of project OROG3NY), as well as the Grant Agency of the Czech Republic (No. 21-25710). The project CzechGeo/EPOS No. LM2015079 of the MEYS funded the MOBNET station pool.
    Beschreibung: Published
    Beschreibung: 671412
    Beschreibung: 1T. Struttura della Terra
    Beschreibung: JCR Journal
    Schlagwort(e): joint inversion ; seismic receiver functions ; gravity anomalies ; Ivrea Geophysical Body ; Ivrea-Verbano Zone ; continental crust ; intra-crustal structure ; 04.01. Earth Interior ; 04.06. Seismology
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 11
    Publikationsdatum: 2022-11-22
    Beschreibung: A realistic view of the Universe
    Beschreibung: Earth Science observations and the Borexino and KamLAND geoneutrino experiments provide clues on the role of aether in the evolution of the Earth, planets, and all other universal structures. Analysis of the problem of storage of aether entering celestial bodies led to a hydrodynamic explanation of gravitation which in turn was found to be closely related to the expanding Earth and to several other phenomena. Variable radius paleogeography provides an approximate assessment of the quantity of ordinary matter added to the planet per time unit, and some inferences about the Earth’s inner energy balance. The aether density, flow rate, and velocity are computed with the help of astrophysics. The origins of cosmological and gravitational redshift are unified under the single cause of gravitation. This is linked to the similar but not interchangeable concept of tired light, which was considered very plausible by cosmologists like Edwin Hubble and Fritz Zwicky. A superluminal speed was calculated for aether at the Earth’s surface. INFN experiments confirm hydrodynamic gravitation and superluminal velocities, and it is possible to identify interrelations of aether parameters with the currently known cosmological parameters H0, G, and c . Unification of hydrodynamic gravitation and the expansion of the celestial bodies through the existence of a minor dissipative force, a non-Newtonian concept, involves a revision of the theories of physics and cosmology, in which the currently accepted laws of physics will be only considered good approximations of a more complex reality.
    Beschreibung: Silvano Gioca
    Beschreibung: Published
    Beschreibung: 1411-1439
    Beschreibung: 1T. Struttura della Terra
    Beschreibung: N/A or not JCR
    Schlagwort(e): Gravitation ; Hydrodynamic Gravitation ; Redshifts ; Expanding Earth ; Evolutionary Universe ; 04.01. Earth Interior
    Repository-Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Materialart: article
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  • 12
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 15-34 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In this paper a multireference constant denominator perturbation theory (CDPT) is developed to reduce incomplete basis set errors arising when solving the Schrödinger equation with a finite basis set. The advantage of this method is that very few basis functions are needed, and all calculations if carried out to high enough order in the perturbation treatment effectively use a complete basis set. As a first step the theory has been restricted to one-particle Hamiltonians and applied to the anharmonic oscillator to study the convergence properties. For perturbation calculations carried out to fifth order, results from Pade approximates show an improvement in accuracy of between one and three orders of magnitude.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 13
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 155-165 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The physical context of the high ionic conductivity of the H+ and OH- ions in aqueous solutions is considered. Quantum dynamical aspects of the mobility of these ions are investigated, especially within the framework of the complex scaling method (CSM). It is argued that the high ionic mobilities under consideration are due to quantum delocalization of the ions as well as mass interference of the H+ ions with water protons. This effect is formally described with the aid of the coherent-dissipative structures, which become spontaneously created in the solution owing to the thermal motion. In particular, (1) a novel connection between the proton transfer rate (as measured by NMR) and the mobilities of the considered ions (as determined by conductivity measurements) is derived. Additionally, (2) a relation connecting the activation energies of the above reaction rates with the ionic mobilities is found. The above relations contain no fitting parameters. Comparisons with experimental results is made, which also reveals the predictive power of the present CSM treatment in the field of microdynamical processes in condensed phases.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 14
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 207-207 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 15
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 655-662 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The aim of this article is to give a practical way for the use of real spherical functions in another frame than the frame in which they have been defined. For instance, we calculate physical properties from a local frame and use them in the general frame, deduced one from the other by Eulerian rotations on the coordinates. The power of the method is in the use of cartesian coordinates and in the definition of a scalar product between these functions to set up the complete vectorial space generated by these representations of the group O3+.
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  • 16
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 309-310 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 17
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 313-313 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 18
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 389-402 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Hubbard theory is an approximation to the Pariser-Parr-Pople theory which presents many of its important features in a relatively simple form. Our Hubbard Hamiltonian employs a single electron-correlation parameter: 0 ≤ x ≡ U/(t + U) ≤ 1, where t is the one-electron hopping integral (the negative of the Hueckel β), and U is the Hubbard one-center, two-electron repulsion parameter. This parameter provides the Hubbard connection between the following: (1)Molecular orbital and valence bond theory(2)The exchange approximation and full CI(3)Conductors and insulators(4)Fermi-Dirac and Boltzmann statistics(5)Normal and superconductorsWe present Hubbard theory in the freeon (spin-free) formulation where each N-electron state is pictorially represented by a Gel'fand diagram which specifies both the orbital configuration and the multiplicity. The simplicity of the freeon formulation makes the Hubbard connection quite transparent.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 19
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 437-448 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We have examined variations in bond orders in conjugated hydrocarbons that follow improvement in MO calculations on going from topological Hückel MO to self-consistent Pariser-Parr-Pople-type calculations. Differences in individual bond orders can be interpreted as pointing to increased weights of selected Kekulé valence structures. Significantly, so indicated valence structures are those with the largest number of formal Kekulé benzene rings or the largest contribution to molecular resonance energy in terms of conjugated circuits.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 20
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 497-508 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Parametrized computational procedures and simplified physical models of molecular reality are often related to one another but are by no means the same thing. With special reference to work by Koutecky and by Cizek, Paldus et al., it is shown here that the PPP model rests on a simple but physically sound electrostatic picture of a molecular π system, and its intrinsic difference from an independent particle model is emphasized. As an illustration of the heuristic power which makes physical models powerful tools of theoretical research, ground state charge transfer GSCT, in situ molecular electronegativity, and the principle of electronegativity equalization are derived within the PPP-CI scheme, no use being made of molecular orbitals, and the assumptions on which the CT theory rests are made explicit.
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  • 21
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The electronic structure of C60 cages are examined by use of the INDO and INDO/CI methods. The calculated spectrum of Buckminsterfullerene has one allowed low-lying band at 27,300 cm-1, to be compared with an experimental value of 25,900 cm-1. These calculations suggest that other cage structures are not stable, or they are not ground state singlets.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 22
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 663-677 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An extension of the IPPP (inner projections of the polarization propagator) method to theoretically analyze transmission mechanisms of indirect nuclear spin-spin couplings is presented. The localization technique used is modified so that all the canonical molecular orbitals of a compound may be localized to represent chemical bonds, lone pairs, and the corresponding antibonding molecular orbitals. These localized molecular orbitals, together with the polarization propagator, are used to obtain an intuitive picture of how a coupling is generated as a sum of terms, each one consisting of two particle-hole single excitations. This picture can be used to identify underlying transmission mechanisms and quantitatively evaluate their importance toward the total coupling. The paramagnetic spin-orbit and the spin-dipole interactions are studied in detail.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 23
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 701-711 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A computational scheme based on a “mixed basis set” approach is applied to the study of the structure and the energetics in proton transfer systems. Five hydrogen-bonded systems of the type (CH3HnA ‥ H ‥ BHmCH3)+, where A and B can be N, O, or S, have been investigated with various minimal and extended basis sets. Calculations with the extended basis set yield double-well potential energy curves, which the minimal basis set is unable to reproduce. Calculations with the mixed basis set, constructed from an extended basis set on the atoms engaged in the hydrogen transfer part and a minimal basis set on the rest of the molecule, give predictions of geometries, potential energy curves, and relative energies similar to the results from the extended basis set. Inclusion of polarization functions in the mixed basis set becomes essential in systems that contain third row atoms. This scheme should become useful in studies of large molecules in which different parts can be represented at different levels of computational complexity.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 24
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 773-783 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: This paper explains a method for finding saddle points on a multidimensional surface and shows how it may be used to define saddle-point seeking curves that have properties similar to well-known orthogonal trajectories. It is shown that a gradient extremal is a special case of one of these curves, and its chemical significance as the path, defined by local criteria, which starts from a stable structure and leads to a transition state, is discussed briefly in relation to the intrinsic reaction coordinate. It is emphasized that this theory gives a natural method for locating points that have Hessians of similar structure to those of transition states.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 25
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 753-771 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Explicit equations for the constants a and b of the energy as the average expectation value for the minimal domain of states giving the Roothaan energy functional are derived in terms of the total spin value and the “seniority” quantum number. The state with off-diagonal long-range order can appear in the framework of the Roothaan scheme for the quasidegenerate system as an alternative to the Hund rule. Admissible many-electron states are established for all configurations of the icosahedral symmetry group systems, and corresponding a and b coefficients are calculated.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 26
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 811-819 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The correlation potential is computed for two electron atomic ions with atomic numbers from 1 to 10 using the charge density reconstructed from a natural orbital expansion of a Kinoshita-like atomic wave function. Over the wide range of densities involved, the correlation potentials are not even approximately a local function of the density.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 27
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 41-53 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In this paper, the symmetrized basis function method is extended and used for the classification of the total spin states of many-electron systems. The reduction matrix, which is expressed as a series of products and direct products of matrices is derived. It is very advantageous that the method can be completed by computer. As an example, the reduction matrix for a 5-electron system calculated by IBM PC computer and the classification of the total spin states is presented.
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  • 28
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 75-83 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In this paper, the TST-CEQ calculated results including the reactive cross sections and rate constants for the Cl + HCl reaction at the specified vibrational state of the HCl are presented. It is shown that the oscillatory behavior of the system in the three-dimensional world does not appear, and the larger the vibrational quantum number of HCl, the smaller the cross sections ¯QTST-CEQ (E, ν) are at a given total energy used in the calculations, but the larger the reactive rate, constants KTST-CEQ (T, ν) are at a given temperature. The KTST-CEQ (T, v) is the same as when first published, and the average reactive rate constants KTST-CEQ (T) are close to the ones by Garrett and Schatz et al.
    Zusätzliches Material: 4 Ill.
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  • 29
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 30
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 383-388 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A formalism is suggested of the so-called local symmetricized orbitals to be used for the construction of a symmetricized basis in molecular electronic structure calculations. The local symmetricized orbitals are defined as additive contributions to the symmetry orbitals of a molecule that arise from symmetry operations of a corresponding atom. The local symmetricized orbitals are transformed according to the irreducible representations of the molecular symmetry group. This approach appears to be most suitable for the optimization of quantum mechanical calculations accounting for the spatial symmetry of compounds under consideration. This fact is due to the formalism of the local symmetricized orbitals that explicitly accounts for the local symmetry of basis function centers, which is essential for such optimization.
    Zusätzliches Material: 1 Ill.
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  • 31
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 173-179 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: This short review concerns the protonation of Schiff bases by halogenic or carboxylic acids with a bias toward the chromophore of visual and bacterial rhodopsins. It is pointed out that the weak acids available in these pigments could not protonate the retinyl Schiff base 100% and that a supporting mechanism is needed to achieve full protonation. Our Fourier transform infrared studies both at room and low temperatures relating to this problem are summarized, and the propable role of water is emphasized.
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  • 32
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 215-219 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The application of the MBPT in the localized representation requires that both the occupied and the virtual orbitals obtained by the canonical HF equation should be localized. The localization of the occupied orbitals is straightforward in general by any localization method. It is shown that by using Boys' method the localized virtual orbitals are spatially well separated and transferable not only in minimal basis sets.
    Zusätzliches Material: 4 Ill.
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  • 33
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 231-238 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Cis-trans photoisomerization of ethylene, some of its methyl and fluoro derivatives, methaniminium, and aminoborane was studied and twisted biradical geometries of these molecules in So, S1, and S2 states were optimized using the half-electron version of the MNDO method with configuration interaction. The results are quite satisfactory, in good agreement with available ab initio data.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 34
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 279-282 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: New possibilities of the spin-extended Hartree-Fock method in determining the sequence of energy levels are analyzed and demonstrated by the example of some oxygen-contained compounds.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 35
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 395-417 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The one-electron density matrix (DM) of crystalline systems is discussed, especially concerning its longrange behavior; reference is made throughout to systems treated at a Hartree-Fock-LCAO-SCF level of approximation. The analysis is performed on the assumption of generally smooth behavior of eigenvalues and eigenvectors in k (reciprocal) space, so that they can be expressed by means of a truncated Fourier expansion. This assumption allows us to obtain analytic approximations for the DM, on the basis of the information collected at a few, suitably selected sampling k points. It is therefore possible at the same time to discuss the influence of structural parameters (dimensionality of the system, existence and shape of the Fermi surface, structure of the chemical bonds) and to set up a computational scheme that is general and simple enough.
    Zusätzliches Material: 5 Ill.
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  • 36
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 461-486 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: This study is a unified approach to quantum theories of polyacen carcinogenesis. Part I discusses the M, L, and B regions theory. Although the M region of polyacens is much less reactive than is the K region, the chemical reactivity of these two regions parallels each other. Consequently, the K-L Pullman's theory may be reformulated by replacing the K region by the M region. The M-L regions theory improves all the quantum structure-carcinogenic activity relationships obtained previously in the K-L framework. Moreover, it would appear that in these correlations, the most important role is played by nonconcerted electrophilic reactions. We suggest that the M-L modified Pullman's theory and the Bay (B) region theory, proposed by Jerina et al., are related to different steps of the metabolic activation mechanism leading to ultimate carcinogen: the first step for the Pullman's theory and the carbocation step for the theory of the Bay region. We have termed the “M, L and B regions theory” as this unified approach to the problem of polyacens carcinogenesis.
    Zusätzliches Material: 8 Ill.
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  • 37
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 38
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 501-520 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The role, and limitations, of the fundamental physical quantities used in our current system of dosimetry for the protection of individuals against the hazardous effects of ionizing radiation is discussed briefly. A major limitation is the inability to correlate biological data, in a unified way, as a function of linear energy transfer with the consequent necessity for quality factors.From consideration of the various interaction processes undergone by charged particles in the equilibrium slowing down spectra generated by the incident radiation field, it is shown that good correlation of biological effects, for all radiation types, can be achieved in terms of linear primary ionization. The implication is that delta-ray effects play at most a very minor role, at moderate fluences, and that, consequently, the absorbed dose is an unsuitable parameter for describing radiation effects. Structure in the radiosensitive targets is observed to have a critical dimension of about 2 nm. It occurs only when double-stranded DNA is present and the magnitude of the inactivation probability is consistent with double-stranded breaks being the significant lesion. Calculation is made of the yield of lesions as a function of the mean free path for primary ionization.Differential spectra of radiation quality are obtained for monoenergetic electrons (0.2 keV to 30 MeV); for characteristic X-rays from carbon, aluminium, neon, potassium, copper, silver, and tungsten; for 50 kV X-rays, 250 kV X-rays, 241Am, 137Cs, and 60Co gamma rays; and for neutrons with energies between 0.1 and 50 MeV. Damage by electrons is shown to be predominant at the ends of their tracks between 50 and 200 eV, whereas this is not so for the proton recoil spectrum generated by neutrons above 1 MeV.Proposals are made for a unified system of dosimetry that is independent of radiation type and that obviates the need for quality factors. The method is thought to be of general applicability to irradiations by nuclides incorporated into mammalian cells, by ingested emitters, and by external sources.
    Zusätzliches Material: 6 Ill.
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  • 39
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 597-605 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: By a way of partitioning of Mulliken overlap populations, the hybrid orbitals of central atoms and ligands are obtained by the CNDO method. The dipole moments of some hybrids are calculated using the hybrid orbitals obtained, and they are mostly in accordance with experimental values. In addition, overlap integrals may be decomposed into components, and then σ, π, and δ hybrid orbitals can be obtained.
    Zusätzliches Material: 2 Ill.
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  • 40
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 611-611 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 41
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 653-664 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Five energy hypersurfaces of the most examined pericyclic reactions have been investigated by using ab initio SCF, CASSCF, and the semiempirical AM1 methods. The systems are H4, H6, C3H6, C4H4, and C3OH4. Stationary points and their sets of harmonic vibrational frequencies have been calculated by means of analytical gradient techniques in the frameworks of the respective approaches. ZPE corrected energy barriers are based on single-point calculations including dynamical correlation corrections by CAS-CI(SD)+DC, CASCEPA, or MP2.
    Zusätzliches Material: 6 Tab.
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  • 42
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 43
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In order to understand the interaction mode of benzodiazepine ligands with their peripheral binding sites, the structural and electronic properties of a benzodiazepine Ro 5-4864, Alpidem, PK 11195, and some analogs are characterized at the ab initio molecular orbital level. Conformational and electronic data, with a particular emphasis on electrostatic aspects, i.e., molecular electrostatic potentials, Mulliken atomic charges, and potential-derived charges, are used as input within molecular superimpositions to elaborate the pharmacophoric elements for the peripheral benzodiazepine ligands. A putative three-dimensional (3-D) steric and electronic model is proposed.
    Zusätzliches Material: 11 Ill.
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  • 44
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 27-34 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The molecular transform is an alternate means of considering numerical representations of molecules in a manner designed to generate indices that can be related to structural and physiochemical parameters. The literature has shown that the transform, actually the Fourier transform, is operable on representations such as Cartesian coordinates or graphically derived depictious reflected by adjacency or distance matrices. The resulting curve may be used to give a binary index of the molecule or integrated to give an area-related index; either of these indices may be used as a correlation parameter in structure-activity studies. In this instance the individual bond distance matrices of a series of structurally diverse compounds served as input for a transform program. The derived index was then used to correlate both physical property and pharmacological activity indices for the series; correlation coefficients were comparable to those reported for the valence molecular connectivity parameter of Kier and Hall. The study also showed that lower correlation coefficients resulted when the index was based on the transform of hydrogen-suppressed structures.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 45
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 263-276 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An algorithm for locating stationary points corresponding to local minima and transition states on potential energy surfaces is further analyzed. This method utilizes local gradient and Hessian (i.e., first and second energy derivative) information to generate a series of “steps” that are followed to the desired stationary point. By designing the step sequence to move energetically downhill in all coordinates, local minima can be found. By stepping uphill along one local eigenmode of the Hessian while minimizing the energy along all other modes, one locates transition states. Key elements of this development are more efficient parameterization of the step vector in terms of quantities that permit the direction (i.e., uphill or downhill), and length of the step to be carefully controlled, and implementation of the ability to explore “side channels” as attractive options occur.
    Materialart: Digitale Medien
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  • 46
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 813-820 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The HeI photoelectron (PE) spectra of No,No-dimethyl-monothiooxamide (1,) its analogue Ns,Ns-dimethylmonothiooxamide (2), dithiooxamide (3), N,N′-dimethyldithiooxamide (4), and N,N,N′,N′-tetramethyldithiooxamide (5) are presented. The results of CNDO/2 calculations, the PE spectra of the related compounds acetamide, thioacetamide, thiourea, and their methyl derivatives, and HeI/HeII intensity considerations are used to assign the spectra.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 47
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 851-857 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We describe our implementation of geometry optimization techniques within the linear combination of Gaussian-type orbitals (LCGTO) approach to local-density functional theory. The algorithm for geometry optimization is based on the evaluation of the gradient of the total energy with respect to internal coordinates within the local-density functional scheme. We present optimization results for a range of small molecules which serve as test cases for our approach.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 48
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 881-889 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 49
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 893-893 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 50
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 19-29 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A procedure for identifying redundancy in the Cartesian force constant matrix is described, and a prescription is given for generating the entire matrix of second derivatives from the minimal set of information. A proof is supplied which demonstrates that the number of nonredundant rows corresponding to a symmetry unique atom is necessarily less than three if the atom is invariant with respect to a symmetry operation of the point group other than the identity or inversion. Furthermore, only one row is required if the atom lies on a threefold or higher-order rotation axis. An application of the procedure to the evaluation of harmonic force constants by numerical differentiation of gradient vectors is briefly described.
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  • 51
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 31-45 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An intermediate neglect of differential overlap (INDO) model for elements of the second transition series is described. Values of exponents for the radial portion of the Slater basis atomic orbitals, the orbital ionization energies, and the beta (or bonding) parameters for these elements are reported. Use of the model to investigate equilibrium geometries, relative energy ordering of geometric isomers, spectroscopic transition energies, energy ordering of state wave functions of different symmetry, trends in dipole moments, and equilibrium stretching frequencies is reported. The results indicate that the INDO method is capable of yielding quality results for species containing atoms of the second transition series.
    Zusätzliches Material: 11 Tab.
    Materialart: Digitale Medien
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  • 52
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 531-547 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We review the nature of the problem in the framework of Rayleigh-Schrödinger perturbation theory (the polarization approximation) considering explicitly two examples: the interaction of two hydrogen atoms and the interaction of Li with H. We show, in agreement with the work of Claverie and of Morgan and Simon, that the LiH problem is dramatically different from the H2 problem. In particular, the physical states of LiH are higher in energy than an infinite number of discrete, unphysical states and they are buried in a continuum of unbound, unphysical states, which starts well below the lowest physical state. Claverie has shown that the perturbation expansion, under these circumstances, is likely to converge to an unphysical state of lower energy than the physical ground state, if it converges at all. We review, also, the application of two classes of exchange perturbation theory to LiH and larger systems. We show that the spectra of three Eisenschitz-London (EL) class, exchange perturbation theories have no continuum of unphysical states overlaying the physical states and no discrete, unphysical states below the lowest physical state. In contrast, the spectra of two Hirschfelder-Silbey class theories differ hardly at all from that found with the polarization approximation. Not one of the EL class of perturbation theories, however, eliminates all of the discrete unphysical states. The best one establishes a one-to-one correspondence between the lowest energy states of the unperturbed and perturbed Hamiltonians, and a one-to-two correspondence for the higher states. We suggest that the EL class perturbation theories would be good starting points for the development of more effective perturbation theories for intermolecular interactions.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 53
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 585-591 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Electron propagator calculations of Sc and Ti ionization energies employing contractions based on atomic natural orbitals reveal the soundness of this approach for choosing basis sets. Errors in total energies greatly exceed those for ionization energies, where contraction errors are reduced to less than 1 mhartree. Systematic improvements involve retention of natural orbitals with lower occupation numbers and augmentation with diffuse and polarization functions.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 54
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 633-644 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Computation is carried out by the motion of the state of a dynamical system. This description unites digital and “neural network” computation. The use of an energy function to understand and to program batch mode computation on feedback networks is reviewed. Recognizing words in continuous speech illustrates the use of a compound network to solve a real-world problem where data arrive continuously over time. A new tool, a Lagrangian formulation, is introduced for studying networks which oscillate, and as a means for formulating problems which need to optimize functional integrals.
    Zusätzliches Material: 1 Ill.
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  • 55
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 681-682 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 56
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 717-719 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 57
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 701-706 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Floating spherical Gaussian basis sets are systematically expanded for a series of small molecules: methane, ammonia, ethane, and acetylene. Localized (nonorthogonal) molecular orbitals are each constructed as a linear combination of up to five functions of the form exp [- (r - R)2/ρ2], where the size ρ and the position R of each function is optimized according to the variation principle. Basis sets are obtained for the C and N cores, the C —; H and N — H bonds, the N lone pair, and the C — C and C—C bonds. Only three to five fully optimized functions are required to describe the main features of each bond orbital, including the negative lobes in the wavefunctions at the heavy atoms and the local maximum in the electron density at the hydrogen atoms. The energies obtained with three basis functions for the core orbitals are intermediate between the results of RHF-SCF calculations with STO-3G and 3-21G basis sets.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 58
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 753-765 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We provide a numerical test of a new approach to calculating approximate interatomic interaction energies based on partial antisymmetry (PA) [Adams, Chem. Phys. Lett. 68, 511 (1979)]. We use spin-coupled products of single determinant atomic wave functions to approximate a particular primitive wave function of the diatomic. Three methods are used: (1) the conventional full antisymmetry (FA) approach, in which the primitive wave function is antisymmetrized and the difference of expectation values of the total energies of the diatomic and atomic systems is calculated, (2) the PA approach, in which only some of the terms of the antisymmetrizer are applied to the primitive wave function, and the energy expressions are simplified based on approximations to the PA theorem [Adams, op. cit.], and (3) a hybrid approach based on a combination of assumptions from the first two approaches, which is comparable to the work of Dacre and McWeeny [Proc. Roy. Soc. London A317, 435 (1970)]. Results are compared with accurate potential curves from the literature. Interaction energies were calculated for the X 1Σ+g states of Ne2, Li2, and Na2, the X 1Σ+ states of LiNa and LiF, the x 3Σ+u states of Li2 and Na2, x 7Σ+u, and x 3Σ+ LiNa at several internuclear distances. In all cases but Ne2, the PA and FA interaction energies are much closer to each other than is either to the accurate reference values. In these cases there is thus no significant penalty exacted for the use of PA over FA, even though it is easier to use. By conventional reasoning, neither the PA nor the Dacre-McWeeny approaches should work at short range or for binding molecules, because they truncate expansions of the antisymmetrizer in the energy expression. Our results provide counter examples to change that expectation, thus providing additional evidence in support of an approximate approach based on the PA theorem.
    Zusätzliches Material: 1 Tab.
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  • 59
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 821-833 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: When a molecular solute is immersed in a polar and polarizable solvent, the electronic wave function of the solute system is altered compared to its vacuum value; the solute electronic structure is thus solvent-dependent. Further, the wave function will be altered depending upon whether the polarization of the solvent is or is not in equilibrium with the solute charge distribution. More precisely, while the solvent electronic polarization should be in equilibrium with the solute electronic wave function, the much more sluggish solvent orientational polarization need not be. We call this last situation “non-equilibrium solvation.” We outline a nonlinear Schrödinger equation approach to these issues. The nonlinearity arises from the self-consistent aspect that the solute electronic Hamiltonian depends on the solvent electronic polarization which is induced by the solute charge distribution. We illustrate the predictions of the theory for electron transfer reactions, ionic dissociations, and solvation dynamics in polar solvents. Special features of interest include activation barriers that differ markedly from standard predictions, and novel solvent dynamical features.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 60
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 843-850 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Previous energy-based criteria for aromaticity developed from one electron eigenvalues (using methods ranging from Huckel to ab initio calculations) have not correlated well with experimentally derived criteria such as χ⊥nlcl or chemical reactivity data, and are particularly poor for heteroaromatic compounds. Previous work has shown that criteria derived from the lowest π molecular orbitals of heteroaromatic compounds correlate well with χ⊥nlcl and chemical reactivity, prompting us to modify Kollmar's procedure for determining aromatic stabilization energies by localizing the lowest π orbital rather than the entire π bonding manifold. This modified procedure was implemented with both the natural (NLMO) and Boys orbital localization methods, and was applied to a set of ten five-membered ring heteroaromatics and to pyridine and its diazine derivatives. The new criterion ΔπL correlated well with χ⊥nlcl (R2 = 0.86 (NLMO); R2 = 0.92 (Boys)) for five-membered rings, and with theoretical measures of aromaticity for both sets of heteroaromatics. The Boys procedure gave better overall correlations and was markedly superior for pyrazole and pyridazine.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 61
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 625-645 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The numerical properties of a two-dimensional integral representation [J. Grotendorst and E.O. Steinborn, Phys. Rev. A 38, 3857 (1988)] of the three-center nuclear attraction integral with a special class of exponential-type orbitals (ETO'S), the B functions [E. Filter and E.O. Steinborn, Phys. Rev. A 18, 1 (1978)] are examined. B functions span the space of ETO'S. The commonly occurring ETO'S can be expressed in terms of simple finite sums of B functions. Hence, molecular integrals for other ETO'S, like the more common Slater-type orbitals, may be found as finite linear combinations of integrals with B functions. The main advantage of B functions is the simplicity of their Fourier transform that makes the derivation of relatively simple general formulas for molecular integrals with the Fourier transform method possible. The integrand of the integral representation mentioned above shows sharp peaks causing, in the case of highly asymmetric charge distributions, slow convergence of the quadrature method used by Grotendorst and Steinborn. New quadrature schemes are presented that use quadrature rules based on Möbius transformations. These rules are well suited for the numerical quadrature of functions that possess a sharp peak at or near a single boundary of integration [H.H.H. Homeier and E.O. Steinborn, J. Comput. Phys., 87, 61 (1990)]. Numerical results are presented that illustrate the fact that convergence of the new quadrature schemes is about a factor two faster in case of highly asymmetric charge distributions.
    Zusätzliches Material: 2 Tab.
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  • 62
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 681-688 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An orbital transformation that minimizes the sum of the squares of the off-diagonal Hamiltonian elements between the singly excited configurations is described. The resulting single-excitations-adapted molecular orbitals (SEAMOS) are found to be very suitable for the description of electronic excited states. The test calculations on the singlet and triplet excited states of the N2, CO, and H2CO molecules are presented.
    Zusätzliches Material: 12 Tab.
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  • 63
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 709-727 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A theoretical model based on physical, chemical, and biochemical mechanisms has been presented to evaluate the yields of DNA strand breaks (single and double) as a function of linear energy transfer (LET) or -dE/dx. Energetic heavy charged particles are considered explicitly to provide a general theory for low- as well as for high-LET radiation. There are three main features of the calculation: (a) track structure considerations for the energy deposition pattern, (b) three-dimensional structure of DNA molecules to provide information on the exact location of damage, and (c) a Monte-Carlo scheme to simulate the diffusion processes of water radicals. To avoid the complexities of a cellular medium, an aqueous solution of DNA is considered in the calculation. When the results of the calculations are compared with experimental measurements of the yields of strand breaks in mammalian DNA (exposed in a cellular complex), reasonable agreement is obtained. However, only those experimental data have been compared where there were no enzyme repair processes. The method of calculation has also been extended to study breaks in higher-order structures of DNA molecules such as chromatin. Specific limitations of the present model have been pointed out for making further improvements.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 64
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 767-786 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Electronic aspects of the catalytic mechanism of liver alcohol dehydrogenase (LADH) are studied with the help of ab initio analytical gradient SCF MO methods. Three points are considered: (i) role of the catalytic zinc; (ii) geometry and electronic structure of the transition state for the hydride transfer reactions; and (iii) factors affecting the energy gap for the hydride transfer step, namely, substrate binding to zinc, reaction field, and serine 48 effects on the potential energy profile. The coordination sphere of the catalytic zinc has been modeled with an ammonia molecule and two SH- groups; complexes with CH3O-, CH3OH, and CH2O have been studied; a (6, 2, 2, 2, 1/6, 2, 1/3, 2) basis set has been used for Zn++; a (5, 2, 1, 1/3, 2) was used for oxygen, carbon, and sulfur; and a (3, 1) was used for hydrogen atoms. The hydride step was studied with two model systems: pyridinium cation/1,4-dihydropyridine coupled to the CH3O-/CH2O reaction, and cyclopropenyl cation/cyclopropene coupled to the CH3O-/CH2O system. For the latter, the role of Ser48 has been studied at the supermolecule level. The calculation on the hydride transfer step has been done at a 4-31G basis set level. The results obtained shed new light on the sources of catalytic activity of liver alcohol dehydrogenases.
    Zusätzliches Material: 4 Ill.
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  • 65
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 839-849 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We present a treatment of chemisorption that uses the Green matrix of the surface and the admolecule, as well as a cluster calculation of a small surface cluster. Since full HF-SCF-band structures with nonlocal exchange are available now for larger systems for a couple of years, it is possible to treat the substrate surface and the admolecule on equal footing. This offers a natural way to solve the embedding problem. We have applied the formalism to the adsorption of H2 on beryllium and show that in contrast to cluster calculations there appears a binding, which is experimentally verified.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 66
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 211-226 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The electronic absorption spectra of 2-, 3-, and 4-vinylpyridines and 1,2-(2,3-dipyridyl), 1,2-(2,4-dipyridyl), 1,2-(3,4-dipyridyl), and 1,2-(4,4-dipyridyl) ethylenes have been investigated in polar and nonpolar solvents. A correlation has been made between the geometry of the molecule and the observed spectrum. Molecular orbital calculations have been carried out using the INDO/S—CI procedure and a limited geometry optimization. The solvent effect at the MO level has been calculated. MO calculations predicted the existence of nπ* transitions that were not observed experimentally. The wave functions of the different CI states were calculated. The experimental transition energy as well as oscillator strength corresponded satisfactorily with the calculated ones. The observed transitions were assigned according to the results of MO calculations.
    Zusätzliches Material: 6 Ill.
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  • 67
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 68
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 251-267 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: From the speculations of G. N. Lewis in 1916, [J. Am. Chem. Soc. 38, 762 (1916)], the spectral predictions of R.S. Mulliken [Nature 122, 505 (1928)], and the quantum mechanical treatment by E. Hückel [Z. Phys. 60, 423 (1930)], the three lowest states of molecular oxygen (3Σg-, 1Δg, and 1Σg+) remained spectroscopic elusives until Gerhard and Lisa Herzberg [G. Herzberg, Nature 133, 759 (1934); L. Herzberg and G. Herzberg, Astrophys. J. 105, 353 (1947); G. Herzberg and L. Herzberg, Astrophys. J. 108, 167 (1948)], precisely defined them by observed infared transitions. The excited singlets remained of interest mainly to atmospheric spectroscopists and astrophysicists, and research on these species was scarce. The discovery in 1963 by A.U. Khan and M. Kasha [J. Chem. Phys. 39, 2105 (1963)] of the simple chemical production of singlet molecular oxygens by the aqueous reaction of hydrogen peroxide and hypochlorite released an explosion of research on the neglected species. Fifteen research symposia and research treatises confirm the broad range of chemical activities of singlet oxygen. The extension to biological systems is now proceeding, with surprising evidence of involvement of natural processes, including the action of singlet oxygen in white blood cell phagocytosis.
    Zusätzliches Material: 14 Ill.
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  • 69
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 115-117 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 70
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 149-161 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The influence of the geometry on the specifics of the electronic structure of Li6 clusters is studied in detail, since planar and three-dimensional lithium hexamers are found to be of comparable stability. The ab initio CI investigation of the Li6 isomers yields almost degenerate lowest singlet and triplet states for certain cluster geometries. Simple criteria for the energy gap between the lowest triplet and singlet state are derived, and their applicability is demonstrated.
    Zusätzliches Material: 5 Ill.
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  • 71
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 371-386 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We propose 10 desirable features or criteria for general purpose methods to be applied to the calculation of a range of spectroscopic properties. We discuss the second-order polarization propagator approximation (SOPPA) in light of these criteria by giving the actual computational expression used as well as a few numerical examples taken from the theory of NMR spectra (magnetic shieldings and spin-spin coupling constants). We demonstrate that SOPPA comes close to fulfilling these criteria.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 72
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 423-436 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A method for analyzing asymmetric top rovibrational bands displaying both blended and resolved features is described. The two-phase computational procedure uses a modified version of the asymmetric rotor-band contour program FASTPLOT to generate a preliminary set of upperstate spectroscopic constants. The parameters are subsequently refined by employing the assigned line-fitting formalism of the ASYROT program using both resolved and blended features. The technique is detailed in a comprehensive analysis of the ν17 band of pyridine. Inclusion of quartic centrifugal distortion constants was found to satisfactorily model a high-resolution (0.004 cm-1) spectrum of this band, yielding a standard deviation of 0.00137 cm-1. The variation in the rotational parameters with vibrational quantum number is examined in terms of possible weak rovibrational perturbations to the ν17 state. An ab initio calculation of the ν17/ν27 Coriolis coupling constant indicates the observed results are consistent with the interaction of these two vibrational states.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 73
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 39 (1991), S. 521-521 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 74
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 321-327 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The method of quasi-classical trajectories on an LEPS hypersurface was used for studying the influence of the exchange of one or both of the hydrogen atoms for deuterium in the reaction H1 + H2Br. As expected, the reaction cross sections of the exchange and abstraction reactions were found to increase if H1 was replaced by D and decrease if H2 was replaced by deuterium. A similar change in the reaction cross sections have also been observed for vibrationally excited reactants. The distribution of vibrational (rotational) energy is related to the ωe (Be) values of the respective reactants and products.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 75
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 339-350 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A three-dimensional potential energy surface for the 2A′ ground state of the system (Ne—H2)+ (2Σ+ in collinear geometry) has been calculated at SCF and CEPA levels. This surface describes the abstraction reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Ne} + {\rm H}^ + _2 \to {\rm NeH}^{\rm + } + {\rm H}, $$\end{document} which is endoergic by 0.57 eV (ΔH00) and has been studied recently by different experimental groups at low collision energies. Our CEPA calculations yield an endoergicity of 0.55 eV (ΔH00). The 2A′ surface has a minimum at collinear geometry with RNe - H = 2.29 a0 and RH—H = 2.08 a0 and a well depth of 0.49 eV relative to Ne + H+2. The effects of electron correlation on the shape of the surface and on the well depth are discussed.An analytic fit of the collinear part of the surface has been constructed based on Simon's proposal of using polynomials in the coordinates (R—Re)/R instead of (R—Re). The fitted potential is used for quantum mechanical scattering calculations with the finite element method (FEM). Preliminary results for reaction probabilities for H+2 in different vibrationally excited states are given and compared to the experimental results.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 76
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 389-394 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A suggested formalism of the local symmetricized orbitals in conjunction with the selection technique for independent blocks of integrals in an original basis is used for a construction of multielectron Hamiltonian matrix elements in the symmetry orbital basis. The optimal molecular electronic structure calculation algorithm with the Hartree-Fock-Roothaan method in the symmetricized basis was obtained as a result. The minimal number of fundamentally distinguished (symmetry attributed) elements both in original and in symmetricized basis is used in the calculations.
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  • 77
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 205-205 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 78
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 79
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 249-256 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The present paper is aimed at differentiability of electronic wave functions, with respect to parametric variables, in the presence of electronic degeneracy. An analysis is made of a wave function, constructed so that it has the largest domain of parameter space in which it is differentiable, with the help of Berry's formula for the geometric phase. In particular, the electronic wave functions, in presence of a double degeneracy in two- and three-dimensional parameter spaces, are studied in detail. It was found that the three-parameter-dependent wave function is differentiable everywhere except along an axis starting from the degenerate point where it is discontinuous. The two-parameter-dependent wave function is differentiable everywhere except at the degenerate point where it is disocontinuous. These singularities are expected to have consequences on wave functions having parametric variables as arguments.
    Materialart: Digitale Medien
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  • 80
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 271-289 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We have carried out an ab initio STO-5G computational analysis of the electrostatic potentials of four structural analogues of the highly toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and four related aromatic systems benzo[a]pyrene, benz[a]anthracene, and two isomeric benzoflavones. These systems, to varying degrees, induce aryl hydrocarbon hydroxylase activity and are believed to interact with the same cytosolic receptor in initiating their biochemical responses. Our present results for the TCDD analogues support and have allowed us to further qualify our early observations regarding factors which are linked to high biological activities in the dibenzo-p-dioxins and structurally similar systems. We find that a high degree of activity appears to require nonoverlapping negative potentials above all or most of the lateral regions, with an observed optimum range of magnitudes. In systems with central oxygens, it is required that the negative oxygen potentials be small and weak; however, oxygen negative regions in the molecule are not necessary for high activity. The observed differences between the potential patterns of the four aromatic systems and those of TCDD and its active analogues may reflect an inherent dissimilarity in the nature of their interactions with the cytosolic receptor. That the carbonyl oxygen negative potential of 7,8-benzoflavone is significantly more negative than its isomer's supports earlier speculation concerning the former's more effective inhibiting effects on metabolic oxidation.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 81
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 167-196 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The electronic structures of undoped and doped copper oxides and other related oxides are investigated on the basis of the N-band Hubbard models. The Hubbard Hamiltonians for clusters of transition metal oxides are exactly diagonalized by the full valence-bond (VB) configuration interaction (CI) method in order to elucidate populations of doped holes, electronic excitation energies, etc. Possible mechanisms of the high-Tc superconductivity for oxide superconductors are discussed on the basis of the calculated results, together with available experiments. The analysis of correlation and spin correlation effects on doped copper oxides indicates theoretical possibilities of new models for organic and organometallic magnetic conductors and superconductors. Organic and organometallic analogs to copper oxides are therefore proposed on the basis of these results.
    Zusätzliches Material: 17 Ill.
    Materialart: Digitale Medien
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  • 82
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 221-240 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Oscillator strengths for transitions involving levels of three spectral series, 3s2 1S → 3snp1P0, 3s3p 1P0 → 3snd 1D, and 3s3p 1P0 → 3sns 1S, have been computed and analyzed for several ions of the MgI isoelectronic sequence (MgI-TiXI). The quantum defect orbital (QDO) formalism has been used throughout, and the results are comparable to those of more complex theoretical procedures.
    Zusätzliches Material: 15 Tab.
    Materialart: Digitale Medien
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  • 83
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 84
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 747-752 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A method is presented for obtaining rapidly convergent upper and lower bounds to the eigenvalues of the Schrödinger equation for one-dimensional and central-field models. The logarithmic derivative of the wave function is written as a Padé approximant and the bounds are obtained by simply counting the real zeroes of the denominator.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 85
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 317-317 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 86
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 349-371 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An historical account is given of the part played by the author in the development of PPP theory in the early 1950s.
    Materialart: Digitale Medien
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  • 87
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 37 (1990), S. 415-422 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The idea of interpreting the semiempirical MO theories from a constrained variational point of view is explored. A density-based approach is developed for calibrating the parameters of useful semiempirical Hamiltonians of molecular electronic structure theory. Results of some numerical experiments with model Hamiltonians of constrained variational origin are reported.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
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  • 88
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Based on the completely optimized S0, S1, and S2 molecular geometries of azulene, the vibronic structure of the S1 ← S0 absorption as well as of the S1 → S0, S2 → S1, and S2 → S0 fluorescences is investigated theoretically within the adiabatic approximation. By means of theory-experiment comparisons, the influence of non-Condon terms and of the Dushinsky effect on the vibronic structure of azulene spectral behavior is discussed. Typical for the S1 ← S0 absorption and the S1 → S0 fluorescence are vibronic transition moment contributions of Condon type, whereas the interpretation of azulene S2 → S1 and S2 → S0 fluorescences is successful only within the scope of the Herzberg-Teller approach by taking into account vibronic coupling terms and, additionally, the Dushinsky effect in the latter case. An analysis of the relevant vibrational modes is given.
    Zusätzliches Material: 3 Ill.
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  • 89
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990) 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 90
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 99-114 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 91
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 129-138 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The polymerization mechanism of tetramethylenes was reinvestigated under inclusion of solvent effects. The approach of a methanol molecule to a borderline diradical, a typical diradical, and a typical zwitterion was studied by a valence, charge, and dipole moment analysis of SINDO1 calculations. Whereas the solvent molecule has no effect on the character of the zwitterion, the borderline diradical was found to switch to a zwitterion at the approach of the methanol molecule if the distance between the donor carbon and the methanol oxygen is below 2 Å. A similar switch of character was observed for the typical diradical at CO distances below 1.5 Å. From energy considerations it is concluded that borderline diradicals can follow a zwitterionic polymerization mechanism in polar solvents, whereas typical diradicals are much less likely to do so.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 92
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 163-171 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We describe a package of some IBM PC programs that may find application in computer-aided molecular design. PCGEOM constructs and visualizes molecular models from bond lengths, bond angles, and dihedral angles, from Cartesian coordinates, or from stored fragments. It may prepare output files to be used as input for other programs, like CNDOB (conventional CNDO/2) or PCMEP using the bond increment (BI) method for the calculation of molecular electrostatic potentials. PCPROT is in preparation and will use Protein Data Bank coordinates to visualize and manipulate protein molecular models. Starting from these, it will calculate electrostatic potentials using the BI method and/or monopoles adjusted to reproduce ab initio values for amino acid residues. FSCF is based on a CNDO-type approximation and uses strictly localized molecular orbitals in order to partition large molecules into a central fragment, a polarizable region, and a fully transferable environment. The partition allows one to handle relatively large systems with up to 200 atoms. To illustrate applications, we present estimation of relative inhibitory potencies of a series of substituted triazines on chicken liver dihydrofolate reductase.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 93
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 209-213 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The possible role of the nonlinear coupling on the character of the dynamics of particle transfer process is investigated. The analysis and solutions of the kinetic equation indicate that nonlinear coupling causes symmetry breaking of particle transfer potential and determines possible equilibrium structure of the system. Dissipative coupling characterizes the rate of the system to reach thermodynamic equilibrium and along with nonlinear coupling and parameters of the system determines in a unique way the resulting equilibrium structure of the system.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 94
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 239-244 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A local electronic-state density in β-cristobalite in the empirical tight-binding approximation has been calculated by the recursion method. In particular, silicon clusters have been considered in β-cristobalite containing up to three coordination spheres of silicon atoms.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 95
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 297-309 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A new form of the generalized master equation for electronic excitation transfer in a partially disordered polymer chain was derived. Within this equation, in order to differentiate the transfer in ordered parts of the partially disordered polymer chain, we decomposed the memory function of electronic excitation into several parts. These parts are memory functions associated with various types of subdynamics of electronic excitation. The partially disordered polymer chain where the disorder is caused by conformational defects is discussed.
    Materialart: Digitale Medien
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  • 96
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Extended Hückel band calculations, frontier crystal orbital analysis, and degenerate-level perturbation theory are used to evaluate the effect inclusion of bulk-layer interactions has on the relative stabilities of ordered overlayers. Five patterns of hydrogen atoms chemisorbed on unreconstructed graphite (11% coverage) are examined for the Bernal (ABABAB…) and registered (AAA…) three-dimensional stackings. The single-layer two-dimensional approximation for graphite is found not to be entirely satisfactory for the type of chemisorption pattern stability questions addressed in this paper.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 97
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 867-867 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 98
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 623-640 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A new formalism has been developed in order to evaluate intermolecular interaction energies for organometallic complexes including electrostatic, polarization, and orbital contributions based on extended Hückel molecular orbital (EHMO) theory. The electrostatic interaction is evaluated using (i) a multipolar expansion of EHMO charge density, or (ii) by calculating directly the electrostatic integrals in the basis of atomic orbitals. The polarization effects are evaluated by introducing a perturbation into the Hamiltonian. The orbital interaction is calculated by considering a supermolecule made of the organometallic substrate and a model electrophile or nucleophile. To provide the shortest possible response time on an interactive computer graphics facility, this model should require the minimum amount of computer time, which explains why approximate procedures are used to evaluate the dominant contributions to the interaction energies. Preliminary results show that these interaction energies lead to reaction potentials in good agreement with experiment for a broad series of nucleophilic and electrophilic addition or substitution reactions involving organometallic complexes. In addition, it is shown that the method can easily be extended for the calculation of solvent effects. To this end, developments considering the supermolecule surrounded by a polarizable continuum are in progress.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 99
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 419-433 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The one-electron density matrix (DM) of a number of crystalline systems - lithium, graphite, boron nitride, silicon, and beryllium - are considered here, as resulting from Hartree-Fock-SCF-LCAO calculations. The influence of structural and computational parameters is discussed. It is shown in particular why the structure of chemical bonds in semiconductors leads to an oscillating long-range behavior of the DM, similar to that observed in metals, where these oscillations are related to the very existence of a Fermi surface. Concerning computational parameters, the influence of the density of sampling k points and of basis set on the calculated DM is considered; it is shown that the choice of the basis set is not a very critical one as far as the DM range is concerned. Some critical aspects of the interrelation between DM range and exchange part of the Fock Hamiltonian are analyzed.
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
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  • 100
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 38 (1990), S. 497-497 
    ISSN: 0020-7608
    Schlagwort(e): Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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