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  • Computational Chemistry and Molecular Modeling  (8,042)
  • 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology
  • Inversion
  • Wiley-Blackwell  (8,045)
  • Seismological Society of America  (8)
  • Wiley  (5)
  • 3
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  • 1
    facet.materialart.
    Unknown
    Seismological Society of America
    Publication Date: 2017-04-04
    Description: Mt. Vesuvius is a worldwide known active volcano located in Southern Italy, east of the city of Napoli. Its last eruption occurred in 1944, ending a continuous open-conduit activity that lasted for more than three centuries. After then the volcano entered into a quiescent phase. Nonetheless, the explosive style of its past activity and its proximity to densely populated areas make Mt. Vesuvius one of the most dangerous volcanoes in the world. For this reason, a comprehensive monitoring program was established, with the goal of early detection of any possible signals of unrest.
    Description: Published
    Description: 809-816
    Description: 5V. Sorveglianza vulcanica ed emergenze
    Description: JCR Journal
    Description: restricted
    Keywords: seismic array ; volcanic seismicity ; array methods ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
    Publication Date: 2017-04-04
    Description: In this work, we present regional maps of the inverse intrinsic quality factor (Qi −1), the inverse scattering quality factor (Qs −1) and total inverse quality factor (Qt −1) for the volcanic environment of Deception Island (Antarctica). Our attenuation study is based on diffusion approximation, which permits us to obtain the attenuation coefficients for every single couple source-receiver separately. The data set used in this research is derived from an active seismic experiment using more than 5200 offshore shots (air guns) recorded at 32 onshore seismic stations and four ocean bottom seismometers. To arrive at a regional distribution of these values, we used a new mapping technique based on a Gaussian space probability function. This approach led us to create ‘2-D probabilistic maps’ of values of intrinsic and scattering seismic attenuation. The 2-D tomographic images confirm the existence of a high attenuation body below an inner bay of Deception Island. This structure, previously observed in 2-D and 3-D velocity tomography of the region, is associated with a massive magma reservoir. Magnetotelluric studies reach a similar interpretation of this strong anomaly. Additionally, we observed areas with lower attenuation effects that bear correlation with consolidated structures described in other studies and associated with the crystalline basement of the area. Our calculations of the transport mean-free path and absorption length for intrinsic attenuation gave respective values of ≈950 m and 5 km, which are lower than the values obtained in tectonic regions or volcanic areas such as Tenerife Island. However, as observed in other volcanic regions, our results indicate that scattering effects dominate strongly over the intrinsic attenuation.
    Description: This work has been partially supported by the Spanish project Ephestos, CGL2011–29499-C02–01, by the EU project EC-FP7 MEDiterranean SUpersite Volcanoes (MED-SUV), by the Basque Government researcher training program BFI09.277 and by the Regional project ‘Grupo de Investigaci´on en Geof´ısica y Sismolog´ıa de la Junta de Andaluc´ıa, RNM104.’ Edoardo del Pezzo was partly supported by DPC-INGV projects UNREST SPEED and V2 (Precursori).
    Description: Published
    Description: 1957-1969
    Description: 3.1. Fisica dei terremoti
    Description: 3.6. Fisica del vulcanismo
    Description: JCR Journal
    Description: restricted
    Keywords: Seismic attenuation; ; Seismic tomography ; Volcano seismology ; Wave scattering and diffraction ; Wave propagation ; 04. Solid Earth::04.06. Seismology::04.06.07. Tomography and anisotropy ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 3
    Publication Date: 2017-04-04
    Description: In the present paper, we will describe the field survey (Fig. 1) and the data analysis of an experiment carried out to put constraints on the magnitude detection threshold in the area of Campi Flegrei. Results show that seismic radiation emitted from VT seismic events at frequency lower than 2 Hz has a high detection threshold (minimum magnitude around 1.5). In the range between 2 and 20 Hz, VT events with magnitudes smaller than about 0.5 have a high probability to be undetected. This result indicates that noise reduction through borehole stations and/or small arrays is essential for an accurate seismic monitoring in the Campi Flegrei area.
    Description: Published
    Description: 190-198
    Description: 3.1. Fisica dei terremoti
    Description: JCR Journal
    Description: restricted
    Keywords: seismic noise ; magnitude detection ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 4
    Publication Date: 2017-04-04
    Description: The peculiar source characteristics of long-period seismic events (time persistency of the source, low-frequency peaks in the source spectrum, absence of high-frequency radiation) prevent the formation of a definite high-frequency coda in the seismograms. In contrast, this is well formed in volcano–tectonic quakes. For this reason, the widely used duration magnitude scale that is based on the proportionality between the energy and the coda duration cannot be used for long-period estimation. In observatory practice, the long-period magnitude is sometimes estimated using the same duration magnitude scale, leading to confusing results. In this report, we show a new method to estimate the magnitude of long-period events that generally occur for volcanoes, with some application examples from data for Mt Etna (Italy), Colima Volcano (Mexico) and Campi Flegrei (Italy).
    Description: Published
    Description: 911-919
    Description: 3.1. Fisica dei terremoti
    Description: JCR Journal
    Description: restricted
    Keywords: Earthquake source observations; ; Volcano monitoring ; Volcano seismology ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 5
    Publication Date: 2017-04-04
    Description: The complex volcanic system of Tenerife Island is known to have a highly heterogeneous character, as recently confirmed by velocity tomography.We present new information derived from intrinsic quality factor inverse maps (Qi −1), scattering quality factor inverse maps (Qs −1) and total quality factor inverse maps (Qt −1) obtained for the same region. The data set used in this work is the result of the analysis of an active seismic experiment carried out, using offshore shots (air guns) recorded at over 85 onshore seismic stations. The estimates of the attenuation parameters are based on the assumption that the seismogram energy envelopes are determined by seismic energy diffusion processes occurring inside the island. Diffusion model parameters, proportional to Qi −1 and to Qs −1, are estimated from the inversion of the energy envelopes for any source–receiver couple. They are then weighted with a new graphical approach based on a Gaussian space probability function, which allowed us to create ‘2-D probabilistic maps’ representing the space distribution of the attenuation parameters. The 2-D images obtained reveal the existence of a zone in the centre of the island characterized by the lowest attenuation effects. This effect is interpreted as highly rigid and cooled rocks. This low-attenuation region is bordered by zones of high attenuation, associated with the recent historical volcanic activity. We calculate the transport mean free path obtaining a value of around 4 km for the frequency range 6–12 Hz. This result is two orders of magnitude smaller than values calculated for the crust of the Earth. An absorption length between 10 and 14 km is associated with the average intrinsic attenuation parameter. These values, while small in the context of tectonic regions, are greater than those obtained in volcanic regions such as Vesuvius or Merapi. Such differences may be explained by the magnitude of the region of study, over three times larger than the aforementioned study areas. This also implies deeper sampling of the crust, which is evidenced by a change in the values of seismic attenuation. One important observation is that scattering attenuation dominates over the intrinsic effects, Qi being at least twice the value of Qs.
    Description: This work has been partially supported by the Spanish project Ephestos, CGL2011-29499-C02-01, by the EU project EC-FP7 MEDiterranean SUpersite Volcanoes (MED-SUV), by the Basque Government researcher training program BFI09.277 and by the Regional project ‘Grupo de Investigaci´on en Geof´ısica y Sismolog´ıa de la Junta de Andaluc´ıa, RNM104’. EdP has been partly supported by DPC-INGV projects UNREST SPEED and V2 (Precursori).
    Description: Published
    Description: 1942-1956
    Description: 3.1. Fisica dei terremoti
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: restricted
    Keywords: Seismic attenuation ; ; Seismic tomography; ; Volcano seismology ; Wave propagation. ; 04. Solid Earth::04.06. Seismology::04.06.07. Tomography and anisotropy ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis
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  • 6
    Publication Date: 2017-04-04
    Description: We present the first application of a time reverse location method in a volcanic setting, for a family of long-period (LP) events recorded on Mt Etna. Results are compared with locations determined using a full moment tensor grid search inversion and cross-correlation method. From 2008 June 18 to July 3, 50 broad-band seismic stations were deployed on Mt Etna, Italy, in close proximity to the summit. Two families of LP events were detected with dominant spectral peaks around 0.9 Hz. The large number of stations close to the summit allowed us to locate all events in both families using a time reversal location method. The method involves taking the seismic signal, reversing it in time, and using it as a seismic source in a numerical seismic wave simulator where the reversed signals propagate through the numerical model, interfere constructively and destructively, and focus on the original source location. The source location is the computational cell with the largest displacement magnitude at the time of maximum energy current density inside the grid. Before we located the two LP families we first applied the method to two synthetic data sets and found a good fit between the time reverse location and true synthetic location for a known velocity model. The time reverse location results of the two families show a shallow seismic region close to the summit in agreement with the locations using a moment tensor full waveform inversion method and a cross-correlation location method.
    Description: Published
    Description: 452-462
    Description: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Description: JCR Journal
    Description: reserved
    Keywords: Volcano seismology ; Computational seismology ; Wave propagation ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 7
    Publication Date: 2017-04-04
    Description: We present the first application of a time reverse location method in a volcanic setting, for a family of long-period (LP) events recorded on Mt Etna. Results are compared with locations determined using a full moment tensor grid search inversion and cross-correlation method. From 2008 June 18 to July 3, 50 broad-band seismic stations were deployed on Mt Etna, Italy, in close proximity to the summit. Two families of LP events were detected with dominant spectral peaks around 0.9 Hz. The large number of stations close to the summit allowed us to locate all events in both families using a time reversal location method. The method involves taking the seismic signal, reversing it in time, and using it as a seismic source in a numerical seismic wave simulator where the reversed signals propagate through the numerical model, interfere constructively and destructively, and focus on the original source location. The source location is the computational cell with the largest displacement magnitude at the time of maximum energy current density inside the grid. Before we located the two LP families we first applied the method to two synthetic data sets and found a good fit between the time reverse location and true synthetic location for a known velocity model. The time reverse location results of the two families show a shallow seismic region close to the summit in agreement with the locations using a moment tensor full waveform inversion method and a cross-correlation location method.
    Description: In press
    Description: (11)
    Description: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Description: JCR Journal
    Description: reserved
    Keywords: Volcano seismology ; Computational seismology ; Wave propagation ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis
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  • 8
    Publication Date: 2017-04-04
    Description: Stress can undergo rapid temporal changes in volcanic environments, and this is particularly true during eruptions. We use two independent methods, coda wave interferometry (CWI) and shear wave splitting (SWS) analysis to track stress related wave propagation effects during the waning phase of the 2002 NE fissure eruption at Mt Etna. CWI is used to estimate temporal changes in seismic wave velocity, while SWS is employed to monitor changes in elastic anisotropy. We analyse seismic doublets, detecting temporal changes both in wave velocities and anisotropy, consistent with observed eruptive activity. In particular, syn-eruptive wave propagation changes indicate a depressurization of the system, heralding the termination of the eruption, which occurs three days later.
    Description: Published
    Description: 1779-1788
    Description: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Description: JCR Journal
    Description: reserved
    Keywords: Interferometry ; Seismic anisotropy ; Volcano seismology ; Volcano monitoring ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 9
    Publication Date: 2017-04-04
    Description: IEEE Standard for Local and Metropolitan Area Networks (hereafter IEEE 802.16; online at http://standards.ieee.org/getieee802/802.16.html) is one of the most promising mobile and fixed broadband wireless access technologies for next-generation all-IP networks in the 3.5 GHz band (European spectrum profile). Commonly known as Universal WiMAX (worldwide inter-operability for microwave access), this access technology reaches a high bit rate and covers large areas with a single base station, making it possible to offer connectivity to end users in a cost-effective way. A further useful property of the WiMAX technology is that the transmission can be used both in line-of-sight (LOS) and non-line-of-sight (NLOS) environments, allowing highly feasible communications (WiMAX Forum 2004). Thanks to these features, IEEE 802.16 opens the way to the use of wireless technologies in the environmental monitoring of areas such as seismic and volcanic zones.
    Description: European Community’s Sixth Framework Programme, Contract no. IST-034622-IP
    Description: Published
    Description: 411-419
    Description: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Description: JCR Journal
    Description: reserved
    Keywords: WiMAX ; volcano monitoring ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.06. Seismology::04.06.10. Instruments and techniques
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 10
    Publication Date: 2017-04-04
    Description: We have implemented a method based on an unsupervised neural network to cluster the waveforms of very-long-period (VLP) events associated with explosive activity at the Stromboli volcano (southern Italy). Stromboli has several active vents in the summit area producing together more than 200 explosions=day. We applied this method to investigate the relationship between each vent and its associated VLP explosive waveform. We selected 147 VLP events recorded between November and December 2005, when digital infrared camera recordings were available. From a visual inspection of the infrared camera images, we classified the VLPs on the basis of which vent produced each explosion. We then applied the self-organizing map (SOM), an unsupervised neural technique widely applied in data exploratory analysis, to cluster the VLPs on the basis of their waveform similarity. Our analysis demonstrates that the most recurrent VLP waveforms are usually generated by the same vent. Some exceptions occurred, however, in which different waveforms are associated with the same vent, as well as different vents generating similar waveforms. This suggests that the geometry of the upper conduit-vent system plays a role in shaping the recurring VLP events, whereas occasional modest changes in the source process dynamics produce the observed exceptions.
    Description: Published
    Description: 2449–2459
    Description: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Description: JCR Journal
    Description: reserved
    Keywords: Stromboli ; Maps ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 05. General::05.01. Computational geophysics::05.01.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 11
    Publication Date: 2017-04-04
    Description: The Colfiorito Basin is a small intramountain depression in the southern section of the Northern Apennine chain that is filled with Quaternary alluvial deposits. The presence of soft alluvial deposits has significantly influenced the level of local damage that was caused by two major earthquakes (ML 5.6 and 5.8) belonging to the swarm that started in September 1997. To verify the effects of the basin structure on the predominant frequency of seismic motion, ambient noise measurements were carried out in the Colfiorito Basin during two experiments in May and July of 2002. The horizontal-to-vertical spectral ratios (HVSRs) were calculated for data collected at four profiles in the basin. Array techniques were applied to determine the wave types that composed the noise, to estimate their apparent velocity and azimuth of propagation, and to calculate a velocity-dispersion curve from which a velocity-depth structure was derived. The data analysis shows a high amplification in the HVSR at low frequency. This feature is common to most of the sites, including the reference site, and it is interpreted as being due to weather disturbances. The peak frequencies of the spectral ratio calculated at the sites located in the center of the basin coincide with the theoretically estimated resonance frequencies. The arrayaveraged HVSR calculated for the array located in the middle of the plain has a pronounced peak at 0.9 Hz. This corresponds to the peak of the amplification function calculated on the basis of the velocity model deduced from the dispersion analysis. The HVSR method is instead unsuitable for the prediction of the resonance frequencies of sediments in the sites where strong lateral variations of basement topography are present. We measured apparent velocities in the range of 0.3–0.8 km/sec by applying f-k methods to array recordings. These values are compatible with the predominance of surface waves in the noise, as also confirmed by polarization analysis. Both Rayleigh and Love waves are present in the background seismic noise. The results obtained by applying the spatial autocorrelation method to the vertical component of the ground motion recorded at a 240-m-wide circular array deployed in the middle of the basin revealed the presence of Rayleigh waves, and f-k methods combined with polarization techniques revealed the presence of polarized Love waves. The wave-field analysis indicates two main propagation directions: the first is around N100 E in the frequency band of 1.0–2.0 Hz; this radiation can be interpreted as being generated at the east-southeast step borders of the basin. The second main direction is around N300 E in the frequency band of 2.0–3.0 Hz; its source may be a 180-m-deep depression located at the southwest corner of the basin.
    Description: Published
    Description: 490–505
    Description: reserved
    Keywords: NONE ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 12
    Publication Date: 2017-04-04
    Description: We investigate the complex propagation of seismic waves beneath the Campi Flegrei caldera, Italy, using multichannel recordings of artificial explosions. The sources consisted of air gun explosions shot in the Gulf of Pozzuoli at offsets ranging between 3 and 7 km. A multichannel recording device was deployed in the Solfatara crater and consisted of ten vertical-component and two three-component short-period seismometers with a maximum aperture of about 150 m. The zero-lag correlation (ZLC) technique was adopted to estimate horizontal slowness and backazimuth of coherent waves crossing the array. For sources located in the northern sector of the Gulf, with maximum offset 5 km, ray parameters and backazimuths are in agreement with those predicted for the 1D velocity model used for routine locations. For sources at offsets larger than approximately 5 km, the ZLC curves depict prominent maxima associated with a secondary phase propagating with a lower velocity than the first-arrival P wave. Using finite-difference synthetic seismograms generated for a 2D realistic velocity model, we explain these late arrivals in terms of a lateral velocity variation located at depths of about 1 km. Such discontinuity would correspond to a positive V (sub p) anomaly imaged by a recent 3D tomographic study, and interpreted as the submerged southern rim of Campi Flegrei caldera collapsed during the explosive eruption of 12 ky B.P. The small spacing among adjacent shot points allowed simultaneous wave-field decomposition at the source and receiver arrays. Using a modified version of the double-beam method, we retrieve the independent variation of horizontal slowness at both the source and receiver regions. For both cases, we found azimuthal deviations as large as 50 degrees with respect to the great circle path. At the source region, these discrepancies may be interpreted in terms of ray bending at the interface of the aforementioned positive anomaly. At the receiver array, the observed anomalies may be attributed to either velocity variations marking the Solfatara crater rim, or to a near-receiver, low-velocity body whose position would coincide with negative gravimetric anomalies and a high V (sub p) /V (sub s) ratio region inferred by independent geophysical and seismological studies.
    Description: Published
    Description: 440-456
    Description: 3.6. Fisica del vulcanismo
    Description: JCR Journal
    Description: reserved
    Keywords: tomography ; campi flegrei ; wavefield modeling ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology
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  • 13
    Publication Date: 2017-04-04
    Description: The properties of the tremor wave field at Stromboli are analyzed using data from small-aperture arrays of short-period seismometers deployed on the north flank of the volcano. The seismometers are configured in two semi-circular arrays with radii of 60 and 150 m and a linear array with length of 600 m. The data are analyzed using a spatiotemporal correlation technique specifically designed for the study of the stationary stochastic wave field of Rayleigh and Love waves generated by volcanic activity and by scattering sources distributed within the island. The correlation coefficients derived as a function of frequency for the three components of motion clearly define the dispersion characteristics for both Rayleigh and Love waves. Love and Rayleigh waves contribute 70% and 30%, respectively, of the surface-wave power. The phase velocities of Rayleigh waves range from 1000 m/sec at 2 Hz to 350 m/sec at 9 Hz, and those for Love waves range from 800 to 400 m/sec over the same frequency band. These velocities are similar to those measured near Puu Oo on the east rift of Kilauea Volcano, Hawaii, although the dispersion characteristics of Rayleigh waves at Stromboli show a stronger dependence on frequency. Such low velocities are consistent with values expected for densely cracked solidified basalt. The dispersion curves are inverted for a velocity model beneath the arrays, assuming those dispersions represent the fundamental modes of Rayleigh and Love waves.
    Description: Published
    Description: 653-666
    Description: reserved
    Keywords: volcanic tremor ; array ; velocity structure ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology
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  • 14
    Publication Date: 2017-04-04
    Description: In this article we report on the implementation of an automatic system for discriminating landslide seismic signals on Stromboli island (southern Italy). This is a critical point for monitoring the evolution of this volcanic island, where at the end of 2002 a violent tsunami occurred, triggered by a big landslide. We have devised a supervised neural system to discriminate among landslide, explosion-quake, and volcanic microtremor signals. We first preprocess the data using a compact representation of the seismic records. Both spectral features and amplitude-versus-time information have been extracted from the data to characterize the different types of events. As a second step, we have set up a supervised classification system, trained using a subset of data (the training set) and tested on another data set (the test set) not used during the training stage. The automatic system that we have realized is able to correctly classify 99% of the events in the test set for both explosion-quake/ landslide and explosion-quake/microtremor couples of classes, 96% for landslide/ microtremor discrimination, and 97% for three-class discrimination (landslides/ explosion-quakes/microtremor). Finally, to determine the intrinsic structure of the data and to test the efficiency of our parameterization strategy, we have analyzed the preprocessed data using an unsupervised neural method. We apply this method to the entire dataset composed of landslide, microtremor, and explosion-quake signals. The unsupervised method is able to distinguish three clusters corresponding to the three classes of signals classified by the analysts, demonstrating that the parameterization technique characterizes the different classes of data appropriately.
    Description: Published
    Description: 1230-1240
    Description: reserved
    Keywords: NONE ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology
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  • 15
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    In:  Computers and Geosciences, Münster, 3, vol. 28, no. 45, pp. 309-326, pp. L11609, (ISBN 0-471-26610-8)
    Publication Date: 2002
    Keywords: Inversion ; Data analysis / ~ processing ; Non-linear effects ; Discrimination ; C&G
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 1-11 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Roothaan-Hartree-Fock (RHF) calculations are carried out for the ground states of the atoms from helium to xenon using a minimal basis set of Slater-type functions whose principal quantum numbers are allowed to take variationally optimal noninteger values. The resulting energies are substantially superior to those obtained previously under the usual restriction that principal quantum numbers be positive integers. The energy lowering relative to the single-zeta wave functions of Clementi and co-workers ranges from 0.0066 Eh in He to 11.2 Eh in Xe. Our results are superior to those obtained by Höjer using a minimal basis set of unconventional binomially screened basis functions. Noninteger principal quantum numbers benefit d-orbitals the most; physically realistic negative d-orbital energies are obtained in all cases including those transition-metal atoms for which a conventional single-zeta STF basis leads to positive d-orbital energies. © 1997 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 23-27 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An ab initio study on the reaction of the ground state (3D) and the excited state (1D) of Sc+ with methane was performed. Reaction channels on the singlet and triplet potential surface (PES) and the reaction mechanism are examined and discussed. Three regions of the potential surface was studied: the molecular complex, the C(SINGLE BOND)H insertion products, and the transition states for the reaction. Comparisons between singlet and triplet PESs show that the excited state (1D) of Sc+ has more reactivity with methane than does the ground state (3D) due to the spin quantum number conservation with the more stable insertion intermediate. © 1997 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 62 (1997), S. 67-76 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The importance of the hybridization displacement charge (HDC) in describing molecular electrostatic potential (MEP) maps was demonstrated by studying six molecules; pyrazine N-oxide, para-nitropyridine, 5-nitropyrimidine, 3-nitropyridazine, N2, and N2O. It is shown that continuously distributed HDC-corrected Löwdin charges reproduce the MEP features of these molecules, most of which have competing electrophilic sites, in agreement with ab initio results. Further, it is found that for homonuclear diatomic molecules MEP minima can be located properly using HDC-corrected Löwdin (or HDC-corrected Mulliken) continuously distributed charges, but these features cannot be obtained using the conventional Löwdin (or Mulliken) charges. It was shown that the order of molecular electric field (MEF) values near the different electrophilic sites becomes changed when one moves away from the molecules. Thus, pyridine-type nitrogen atoms are the preferred binding sites close to the molecules, while at large distances, effects of oxygen atoms of the NO groups become dominant. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 115-124 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some types of atomic vibrations in a chain of the DNA type constructed of G-C pairs were studied. These are the atomic vibrations of the lateral groups of guanine and N(3)H(1)H(2) of cytosine connected by the hydrogen bond h-b-1 and the vibrations of the centers of masses of bases in the direction parallel to bonds h-b-i, i = 1-3. The vibrations mix partially due to the dependence of the energy of the bond h-b-1 on its length and split into two bands because of the interaction between neighboring base pairs. It was shown that the excitation of the bond h-b-1 results in the splitting off of the two local vibrations and in a small deformation of the chain in the vicinity of the pair with the localized hydrogen bond. The law of the dispersion of band vibrations, values of the split-off frequencies, and degree of poly(dG)-poly(dC) chain deformation were determined. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 273-278 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Analytical solutions to the Yukawa-like screened Coulomb nuclear attraction and electron repulsion molecular basic integrals, as well as to the basic integrals required to compute the virial coefficient, over Gaussian basis functions, are derived and cast into a practical closed form, suitable to interface with modern codes for the calculation of molecular electronic structure. © 1997 John Wiley & Sons, Inc.
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  • 21
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    International Journal of Quantum Chemistry 62 (1997), S. 303-314 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: He I photoelectron (PE) spectra of four carboxylic acids and five esters are measured. Semiempirical and ab initio quantum chemical calculations are used for the interpretation of the spectra. The complex approach which uses empirically established relationships (the dependence of valence electron ionization energies on proton affinities in the gas phase, on the core level ionization energies, and on the structure) was developed. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 323-328 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Simple molecular orbital calculations are employed in searching electronic parameters which may characterize the chemical carcinogens. Using frontier orbitals, the carcinogen-DNA bond formation is described as an electron transfer from the highest occupied molecular orbital (HOMO) of DNA to the lowest unoccupied molecular orbital (LUMO) of the carcinogen. Analysis of the DNA bases units shows that the electron donation occurs preferentially at the guanine site. The calculated low LUMO energy of several carcinogens indicate correctly the electrophilic character of these compounds. The difference between the carcinogen and the ultimate carcinogen is analyzed. Epoxides, free radicals, alkylating agents, and other metabolite forms are studied. A reasonable correlation is found between the LUMO energy and the carcinogenic function. © 1997 John Wiley & Sons, Inc.
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  • 23
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    International Journal of Quantum Chemistry 63 (1997), S. 1107-1122 
    ISSN: 0020-7608
    Keywords: relativistic pseudopotentials ; heavy atoms ; method of molecular calculation ; electronic structure ; Gaussian approximation ; Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Gaussian expansions of the generalized relativistic effective core potential (GRECP) components are reported for elements Hg through Rn. The accuracy of the analytical GRECPs is estimated by calculations of atomic transition energies with the numerical one-configurational wave functions in comparison with Dirac-Fock calculations. The results of the corresponding calculations with the RECPs of other groups are also given. An “averaged error” in the reproduction of the transition energies without the change of the occupation number of the 5d-shell is an order of magnitude smaller than that for the RECPs of other groups. As is demonstrated for the transitions with the change of the occupation number of the 5d-shell in mercury, the largest absolute error of the GRECP is only 1.5-2 times smaller than that of the energy-adjusted pseudopotential (PP) or the RECP of Ross et al. with the same space of explicitly treated electrons. However, the dispersion of these errors is 19⋅10-4 au for the energy-adjusted PP, 35⋅10-4 au for the RECP of Ross et al. and only 4⋅10-4 au for the GRECP. One-configurational spin-averaged calculations of the molecular properties for HgH and HgH+ are carried out and compared with the corresponding results of Häussermann et al.   © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 1107-1122, 1997
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    International Journal of Quantum Chemistry 63 (1997), S. 1123-1131 
    ISSN: 0020-7608
    Keywords: MD simulations ; liquid surface ; formamide ; molecular orientation ; molecular surface density ; Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular dynamics simulations of liquid formamide(HCONH2) were carried out using the GROMOS software. The formamide molecule is represented by all of its atoms with all internal degrees of freedom. In contrast to other simulations dealing with bulk properties, this study focuses on the interface liquid-vacuum for the first time. We show that the molecular plane is tilted out of the surface, exposing the HCO group to the vacuum.   © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 1123-1131, 1997
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    International Journal of Quantum Chemistry 62 (1997), S. 29-45 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The H2 interaction with the Pd dimer and trimer were studied using multiconfigurational self-consistent field (MC-SCF) calculations with the relativistic effective core potential (RECP); the correlation energy correction was included in the extended multireference configuration interaction (MRCI), variational and perturbative to second order. Here, we considered the Pd2 first six states: 3Σ+u, 1Σ+g, 3Πg, 3Δxy, 1Σ+u, and 3Σ+g. For them, the four geometrical approaches included were the side-on H2 toward Pd2, for the hydrogen molecule in and out the Pd dimer plane; the perpendicular end-on H2 toward Pd2; and the perpendicular end-on Pd2 to H2. The Pd2 ground state is 3Σ+u, which only captures H2 in the C2v end-on approach, softly relaxing the H(SINGLE BOND)H bond. The closed-shell 1Σ+g captures the H2 molecule in all the approaches considered: The side-on approach of this state presents deep wells and relaxes the H(SINGLE BOND)H bond, and the end-on approach captures H2 with a relatively longer H(SINGLE BOND)H distance and also a deep well. The 3Πg state was the only one which did not capture H2. For the triangular Pd3 clusters, H2 was approached in the C2v symmetry in and out of the Pd3 plane. In the triangular case, H2 was absorbed in both spin states, with deep wells and relaxing the H(SINGLE BOND)H distance. The linear Pd3 singlet and triplet states capture outside of the Pd3 and break the H(SINGLE BOND)H bond. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 89-96 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We presented a calculation of the total and partial decay widths of vibrational predissociation (VP) of the HeI2 molecule for low initial vibrational excitations from the lowest van der Waals (vdW) state with total angular momentum J = 0. A time-dependent golden rule wave-packet method was employed in our numerical calculations for the decay widths. The computed total decay widths, lifetimes, and rates of VP are in fairly good agreement with those extrapolated from the experimental data available. Predicted total decay widths as a function of initial vibrational levels exhibit a highly nonlinear behavior. These results demonstrate that a quantum mechanical decay mode for low vibrational excitation remains as well. The total propagation time needed in the time-dependent golden rule wave-packet calculations is much shorter than is the lifetime of the predissociation of HeI2. It is shown that the final-state interaction between the fragments is important for determining the final rotational-state distribution (partial decay width). We find that the major peak position in the final rotational-state distribution shifts to lower rotational energy levels with increase of the initial vibrational quantum number, which is evidently different from that for higher vibrational levels. This fact can be clearly explained by the dependence of the amount of kinetic energy released to the product degrees of freedom on the initial vibrational state. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 63 (1997), S. 1065-1078 
    ISSN: 0020-7608
    Keywords: very precise eigenvalues ; very accurate grid method ; general solution for Schrödinger equations ; rapidly convergent treatment for helium eigenvalues ; superconvergence ; optimization of grids ; treatment of continuum ; Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An extension to the theory of Schrödinger equations has been made which enables the derivation of eigenvalues from a consideration of a very small part of geometric space. The concomitant unwanted continuum effects have been removed. The theory enables very convergent or “superconvergent” calculations. In the case of the helium ground state, E=-2.90372437703411987 Eh was obtained from 251 terms. The result is comparable to that from the largest variation calculations so far carried out reinforced by extrapolation techniques. The theory is extensible to atoms and molecules irrespectively of the number of electrons or nuclear centers. In these cases, the advantage of “superconvergent” calculations will be more pronounced than in the case of helium.   © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 1065-1078, 1997
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    International Journal of Quantum Chemistry 62 (1997), S. 239-244 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We calculate the resonant and antibound state energies for a Morse potential with a centrifugal barrier using Siegert boundary conditions. Starting with a complex wave number k (purely imaginary for bound and antibound states), we integrate numerically from the origin up to a matching point using Numerov's method. The inward integration is performed using the corresponding (first-order) Riccati equation. The complex eigenvalues are found by matching the two logarithmic derivatives. We find narrow shape resonances within the well, above the dissociation limit, and broad resonances above the centrifugal barrier. Antibound states are found even with J = 0. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 265-272 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: Numerical experiments with a nonlinear (λχ4) oscillator which has its harmonic frequency changing randomly with time reveal certain interesting features of its dynamics of quantum evolution. When λ = 0, the level populations are seen to oscillate. But, as the nonlinear coupling is switched on (λ 〉 0), a threshold is reached at λ = λc when the evolution is seen to be characterized by an abrupt transition dominantly to the highest available state of the unperturbed (initial) oscillator. It is shown that this transition probability is maximized at a particular value of λ. The time threshold for this transition decreases with increasing nonlinear coupling strength. The numerically obtained structures of the underlying quantum-phase spaces of the linear and nonlinear random oscillators are examined. Possible use of these results in a problem of chemical origin is explored. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 279-289 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Testosterone (17β-hydroxy-4-androsten-3-one) was studied by the semiempirical AM1 and PM3 and ab initio STO-3G*, 3-21G*, and 6-31G* methods. The goals were to compare those methods and to know the electronic structure of the hormone. Full geometry optimization was performed, and two crystal conformers (T1 and T2), and experimental dipole moment in solution were used for comparison. One conformer with a dipole moment similar to the solvated conditions was generated. Total energy, entalphies, dipole moments, charges, electrostatic potentials, and highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbital (LUMO) were calculated. Root-mean-square (RMS) index of the theoretical molecules against T1 and T2 showed best results with the 3-21G* and 6-31G* methods, while AM1 gave better energies than PM3. Dipole moments were directed toward the OH group and the botton face of the A ring. The frontier orbitals were located along the C4-C5 π bond, particularly the LUMO was split between C4 and C5, predicting the action of enzymes at C5 yielding to 5α and 5β-reduced androgens. Electrostatic potentials might be also of biological importance since they are coincidental with the dipole-moment orientation. Finally, it is interesting that the solvatedlike conformer, its properties, and the OH group laid between the same group of T1 and T2 and with a total energy between the crystals and the gas phase or in vacuo conditions. This results might also explain the biology of testosterone and use them to model the hormone-receptor interaction. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 315-322 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two alternative dehydration reactions C(OH)4 → (HO)2CO + H2O and C(OH)4 + H2O → (HO)2CO + 2H2O are studied by ab initio Becke3LYP/6-311 + G** and MP2/6-31G** methods. Calculated energy and geometry characteristics of intermediates and transition states predict a catalytic effect of one water molecule and the exothermism of the transformations. Relevant HF/6-311 + G**, HF/6-31G**, HF/6-31G, and HF/3-21G calculations were performed for comparison. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 97-113 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Restricted geometry optimizations at the ab initio SCF level with the 3-21G basis set were employed to investigate the conformation space of flavone acetic acid (FAA) and its related compounds. All the conformations are produced from a conformation which is, according to our previous work, probably the active conformation in terms of antitumor activity shown by these compounds. Detailed studies on FAA were carried out while only brief discussions are made on the analogs. The main results obtained are that (1) FAA is a very flexible molecule, e.g., with the energy barrier up to about 3 kcal mol-1 from the reference conformation, the important torsional angle τ1 can change from 27.0° to 117.0°, τ2 from -168.0° to 2.0°, and τ3 from -50.0° to 30.0°; (2) the hydrogen-bonding effect plays an important role in determining lower-energy conformations; (3) among all the FAA conformations considered, some are active and some are inactive; (4) it seems that the analogs will have similar behavior to FAA when the torsional angle τ3 is restricted to the values which are around the equilibrium values; and (5) the hypothesis put forward previously has been further developed in this work. Now, we postulate that efficient charge transfers will lower the energy and that proper charge transfers will activate the molecule. There are mainly two different types of charge transfer corresponding to two different types of conformation, which are specified in this article. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 55-65 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We compare geometry configurations, vibrational properties, and electronic structures of (HF)2 in a free state and inside argon atom shells Arn. For the first stage, molecular dynamics calculations for the (HF)2 · Ar62 heterocluster are performed with the help of model potentials HF(SINGLE BOND)HF, Ar(SINGLE BOND)Ar, and Ar(SINGLE BOND)HF. Then, ab initio quantum chemistry analysis is carried out for the smaller systems (HF)2 · Ar15 and (HF)2 · Ar6 when keeping the argon atoms closest to the trapped dimer. We conclude that the hydrogen-bonded complex (HF)2 gains some extra stability inside the argon shells, originating primarily from a decrease of intermolecular distance RFF. Electronic structure calculations are in accord with the changes in dynamical properties, namely, a noticeable increase in the vibrational frequency assigned to the F(SINGLE BOND)F stretching mode (+25 cm-1) and decrease in rms deviations for the corresponding coordinate δFF. In addition to these changes, the argon atoms of the nearest solvent shell donate a small fraction of electron charge which is spent for an increase of population of the antibonding orbital σ*Hf(SINGLE BOND)Ff of the free monomer unit and shift orbital energies primarily of the lone-pair fluorine species. These shifts are greater than the changes due to geometry alterations and the possible inaccuracies of the calculation scheme. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 13-21 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An analysis of the anisotropic Heisenberg model is carried out by solving the Bethe ansatz solution of the model numerically as a function of the anisotropy parameter for finite N. A brief introduction to the limit of the infinite chain is presented. The energy for a few special limiting cases of the anisotropy parameter in the Hamiltonian are worked out. Numerical results for finite cycles as well as for the infinite chain are given. Comparison can then be made with the case of finite increasing N. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 47-53 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The MELD program is employed to evaluate the Slater average potential v(r) felt by an electron at the point r within an atom. The characteristic radius R of the atom is then defined by the classical turning point equation v(R) = -I, where I denotes the first ionization potential of the atom. The atomic radii defined in this way have a close correlation with the van der Waals atomic radii. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 77-88 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Highly accurate upper bounds for several 2Pe states of the Li isoelectronic series obtained by extensive Hylleraas-Cl calculations are given. The best value for the 22Pe state (1s2p2) of Li is -5.21373920 au. The evaluation of the occurring integrals is given explicitly. Additionally, we present some expectation values and isotope energies of the Li isoelectronic series. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 245-259 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An efficient expansion method for the evaluation of VB matrix elements is introduced. The overlaps of VB wave functions of N electrons can be treated as algebrants, i.e., generalized determinants, of N × N matrices. An algebrant can be expanded with subalgebrants of lower orders in a successive way. By choosing Rumer spin bases and appropriately arranging the expansion, it is found that the number of unique subalgebrants involved in the expansion increases in a quite moderate way with N. In contrast to the traditional symmetric group approach, which explicitly utilizes all N! representation matrices, the new strategy incorporates the group theoretical factors in a simple way in the successive expansion. As only the unique subalgebrants are further expanded, the computational effort required by the new strategy scales in a very acceptable manner with the increasing number of electrons. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 62: 245-259, 1997
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    International Journal of Quantum Chemistry 62 (1997), S. 261-264 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Characters of irreducible representations (irreps) of the symmetric group corresponding to the two-row Young diagrams, i.e., describing transformation properties of N-electron eigenfunctions of the total spin operators, have been expressed as explicit functions of the number of electrons N and of the total spin quantum number S. The formulas are useful in various areas of theory of many-electron systems, particularly in designing algorithms for evaluation of spectral density moments. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 291-296 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The geometries and S-H, S-S, and S-C bond dissociation energies for hydrogen sulfide, hydrogen disulfide, methanethiol, dimethyl disulfide, and dimethyl disulfide were calculated with both ab initio (ROHF and MP2), hybrid (BHandH, BHandHLYP, Becke3LYP and Becke3P86), and nonlocal (BLYP and BP86) density functional theory (DFT) methods. In all studies the 6-31 + G(d) basis set is used. The computed results are compared to the experimentally obtained values, targeting the selection of a suitable ab initio or DFT method for the study of these systems. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 62 (1997), S. 297-302 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism and kinetics for the decomposition of β-hydroxypropaldehyde, primary and secondary β-hydroxyketones, were studied by using ab initio RHF/6-31G and RHF/6-31G* methods. The activation barriers of these reactions were refined to be 39.57, 40.10, and 36.80 kcal mol-1 at the MP2/ /RHF/6-31G* level, respectively. The calculated results show that each decomposition is a concerted process with hydrogen transferring and bond breaking via a six-membered cyclic transition state. The thermal rate constants of the decomposition of primary and secondary β-hydroxyketones were obtained by calculating microcanonical probability fluxes through each transition state. It is theoretically confirmed that methyl substitution at the hydroxyl carbon of β-hydroxyketones causes a small enhancement in rates. The theoretical investigations of the mechanism and the rate constants are in agreement with the experimental results. © 1997 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 63 (1997), S. 1079-1089 
    ISSN: 0020-7608
    Keywords: large-order perturbation theory ; lie algebra ; three-body problem ; symbolic computations ; helium atom ; Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of o(4, 2) operator replacements is generalized. As a result, the series whose limiting values when the variable goes to  +∞ should correspond to the two-electron atom energies now have rational coefficients. This generalization allows one also to compute the series for the case of singlet S symmetry, a case which could not be considered in the previous original formulation of the method. Series with rational coefficients for the helium singlet and triplet S ground-state energy are calculated up to order 41 and 45, respectively. Moreover, symbolic computations also allow one to give the first few coefficients of these series for arbitrary values of the nuclear charge Z. Finally, a new method for analytic continuation to the limit  +∞ is presented for the energies of the helium singlet and triplet ground states.   © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 1079-1089, 1997
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    International Journal of Quantum Chemistry 63 (1997), S. 1099-1106 
    ISSN: 0020-7608
    Keywords: metathesis reactions ; bond order ; free valence ; minimum energy path ; nonsynchronization ; Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A few simple atom-transfer reactions (i.e., Ȧ+X-A→A-X+Ȧ) are studied by quantum mechanical ab initio methods. Emphasis is given to the detailed analysis of density matrices rather than to the energetics. Results reveal that during these reactions a small free valence always develops on the migrating atom at the transition state. The barriers in these reactions arise from the greater extent of bond cleavage in the reactant than that of bond formation in the transition state. Analysis of bond orders estimated from bond lengths using Pauling's relation also leads to the fact that the bond-cleavage process is more advanced than is the bond-formation process in these reactions.   © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 1099-1106, 1997
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    International Journal of Quantum Chemistry 57 (1996), S. 7-15 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: The solution of the Schrödinger equation for the d-dimensional hydrogen atom in a d-dependent potential defined by Gauss' law has been studied by the shifted 1/d method and the δ expansion. These methods provide analytical formulas for the eigenvalues and eigenfunctions which have been tested against “exact” numerical values obtained recently. The comparison shows that the results obtained with the analytical expressions are in excellent accord with the numerical ones and, on the other hand, provide a theoretical justification for a proposed empirical expression for the energies of the two-dimensional hydrogen atom with a logarithmic potential energy function. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 57 (1996), S. 17-33 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: An analysis of the structure of the optimized effective Kohn-Sham exchange potential vx and its gradient approximations is presented. The potential is decomposed into the Slater potential vs and the response of vs to density variations, vresp. The latter exhibits peaks that reflect the atomic shell structure. Kohn - Sham exchange potentials derived from current gradient approaches for the exchange energy are shown to be quite reasonable for the Slater potential, but they fail to approximate the response part, which leads to poor overall potentials. Improved potentials are constructed by a direct fit of vx with a gradient-dependent Padé approximant form. The potentials obtained possess proper asymptotic and scaling properties and reproduce the shell structure of the exact vx. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 57 (1996), S. 43-51 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: Analytical exact expressions are obtained for matrix elements of the modified Pöschl-Teller oscillator over different operators including powers of the hyperbolic functions sinh(α x), cosh(α x), and tanh(α x) and the differential operators d/dx and d2/dx2. These expressions are derived using explicitly the Pöschl-Teller eigenfunctions. In addition, several recursion relations connecting different Pöschl-Teller matrix elements are obtained using the factorization and hypervirial techniques. It is shown that these relations can be used to make easier the computation of the matrix elements. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 57 (1996), S. 53-61 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: The D-dimensional Coulomb system serves as a starting point for generating generalized atomic shells. These shells are ordered according to a generalized Madelung rule in D dimensions. This rule together with an Aufbau Prinzip is applied to produce a D-dimensional periodic table. A model is developed to rationalize the ordering of the shells predicted by the generalized Madelung rule. This model is based on the introduction of a Hamiltonian, invariant under the q-deformed algebra Uq(so(D)), that breaks down the SO(D + 1) dynamical symmetry of the hydrogen atom in D dimensions. The D = 2 case (Flatland) is investigated in some detail. It is shown that the neutral atoms and the (moderately) positive ions correspond to the values q = 0.8 and q = 1, respectively, of the deformation parameter q. © John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 57 (1996), S. 137-137 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    International Journal of Quantum Chemistry 57 (1996), S. 1-2 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    International Journal of Quantum Chemistry 57 (1996), S. 123-135 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: Ab initio calculations at the scf level were carried out to compute the polarization potential map (mpp) of the nucleic acid bases: cytosine, thymine, uracil, adedine, and guanine. For this purpose, the Dunning's 9s5p basis set contracted to a split-valence, was selected to perform the calculations. The molecular polarization potential (mpp) at each point was evaluated by the difference between the interaction energy of the molecule with a unit point charge and the molecular electrostatic potential (mep) at that point. meps and mpps for the different molecules were computed with a density of 5 points/Å2 on the van der Waals surface of each molecule, defined using the van der Waals radii. Due to the symmetry of the molecules, only half the points were computed. The total number of points calculated was 558 for cytosine, 621 for thymine, 526 for uracil, 666 for adenine, and 699 for guanine. The results of these calculations are analyzed in terms of their implications on the molecular interactions between pairs of nucleic acid bases. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 57 (1996) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    International Journal of Quantum Chemistry 57 (1996), S. 139-139 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    International Journal of Quantum Chemistry 57 (1996), S. 141-155 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: The matrix differential calculus is applied for the first time to a quantum chemical problem via new matrix derivations of integral formulas and gradients for Hamiltonian matrix elements in a basis of correlated Gaussian functions. Requisite mathematical background material on Kronecker products, Hadamard products, the vec and vech operators, linear structures, and matrix differential calculus is presented. New matrix forms for the kinetic and potential energy operators are presented. Integrals for overlap, kinetic energy, and potential energy matrix elements are derived in matrix form using matrix calculus. The gradient of the energy functional with respect to the correlated Gaussian exponent matrices is derived. Burdensome summation notation is entirely replaced with a compact matrix notation that is both theoretically and computationally insightful. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 57 (1996), S. 157-172 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: The size-extensive quadratic CI method with single(s), double(D), and triple (T) excitations, QCISDT, is compared with QCISD, QCISD(T), CCSDT-n, and CCSDT. It is shown that QCISDT results are more accurate than are either QCISD or QCISD(T) results. In particular, QCISDT turns out to be more stable than are QCISD and QCISD(T) in cases with considerable multireference character. QCISDT and CCSDT results are of similar accuracy with slight advantages for the former method. Since QCISDT is much easier to implement on a computer than is CCSDT, it is an attractive alternative to CCSDT. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 57 (1996), S. 173-182 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: This article presents remarks on the meaning of stopping power and of its magnitude. More precisely, the first set of remarks concerns the connection of stopping power with elements of particle-transport theory, which describes particle transport and its consequences in full detail, including its stochastic aspects. The second set of remarks concerns the magnitude of the stopping power of a material and its relation with the material's electronic structure and other properties. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 57 (1996), S. 219-227 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: For the first hydrogen bond of the guanine-cytosine (G-C) pair, the potential function V(r, R) is found for the nonequilibrium bond length R. A new form of the semiempirical potential function, Clementi's calculations for V(r, R0) and some experimental data are used. New wave functions and energy levels as a function of the H-bond length for the ground and several excited states are obtained. This allows one to obtain frequencies and amplitudes of some vibrations of the G-C pair side groups involved in the formation of the hydrogen bond when the latter is not excited and when it is excited to the first energy level. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 57 (1996), S. 229-233 
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    Topics: Chemistry and Pharmacology
    Notes: Restricted open-shell Hartree-Fock and unrestricted Hartree-Fock calculations of the electric-field gradient in atoms B, N, O, Al, S, and Cl were performed by relieving the spherical symmetric constraint. The Sternheimer's core polarization effect is then automatically taken into account. The orbitals produced by the axial symmetric self-consistent field are found to have axial symmetry of s-d and p-f mixing types. However, the nonequivalence of the three p orbitals also gives rise to ambiguity. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 57 (1996), S. 235-243 
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    Topics: Chemistry and Pharmacology
    Notes: The diagonalization of a class of lattice spin models of a particular structure is first reviewed and secular polynomials for these models are calculated explicitly from the corresponding secular matrices. The structure of the eigenvectors of the given secular matrices is investigated and used to determine the eigenvalues theoretically, and proofs which have not appeared are presented. These results can be compared to the results obtained from the full secular polynomials. © 1996 John Wiley & Sons, Inc.
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    International Journal of Quantum Chemistry 57 (1996), S. 259-259 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    International Journal of Quantum Chemistry 57 (1996), S. 263-263 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    International Journal of Quantum Chemistry 57 (1996), S. 377-389 
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    Topics: Chemistry and Pharmacology
    Notes: The recently introduced set of quadratic ionic and covalent valence indices from changes in the pair-diagonal part of the molecular (Hartree-Fock) two-electron density matrix, ΔΓ(2)(a, b) (orthogonal atomic orbital [OAO] basis set), relative to separated atoms limit (SAL), is extended to cubic valence numbers; they are calculated from the corresponding changes in the three-electron density matrix, ΔΓ(3)(a,b,c). The two- and three-electron indices are given by the corresponding contributions to ΔΓ(2), and ΔΓ(3), which are quadratic and cubic in terms of relevant changes in the one-electron density matrix. The new valence measures are partitioned into one-, two-, and three-center contributions comprising purely ionic (covalent) and mixed ionic-covalent terms. For integral OAO occupations in the SAL, the sum of all three-electron contributions vanishes exactly in the UHF approximation; for fractional occupations, they give rise to a rather small correction to the overall two-electron valence index. The properties of cubic valence numbers are tested on a model three-orbital description of a symmetric (ABA), collinear transition state and on the OQ2 (Q = 1,0, -1) and O2(bond)H+ systems. Preliminary results for B2H6 are also given. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 235-248 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: Extremal pair functions for an n-electron wave function of a closed-shell state are defined as linear combinations of spin-orbital-product pair functions that make some functionals (e.g., r212 or r-112) extremal. They are related to the natural spin geminals in the uncorrelated limit and are useful both for an analysis of wave functions in view of an understanding of the chemical bond and for the treatment of electron correlation. Numerical examples are shown and discussed for He2 as well as the 10-electron systems Ne, HF, H2O, NH3, and CH4. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 287-295 
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    Topics: Chemistry and Pharmacology
    Notes: The generalized Langevin equations are presented by considering such microscopic motions of molecules described by the microscopic Hamiltonian whose potential function is quadratic and internal degree of freedom is multidimensional. Considering the long time behavior of the reactive mode, the Grote-Hynes equation has been derived from the generalized Langevin equations. Furthermore, we have proved that solving the Grote-Hynes equation is equivalent to solving the eigenvalue problem for the whole system, and then the Grote-Hynes treatment coincides with the transition-state theory for the whole system. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 307-320 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: Motivated by McWeeny's pioneering work on the solution of the Schrödinger equation in momentum space and his early treatment of X-ray scattering factors from the electron distribution ρ(r) in both isolated and bonded atoms, the relation between momentum space moments 〈pn〉 and ρ(r) is first developed semiclassically, as in the forerunner of density functional theory, the Thomas-Fermi method. The relation between 〈p〉 and the Dirac-Slater exchange energy prompts the treatment of an exact nonlocal relation between kinetic and exchange energies in Hartree-Fock theory. The Hiller-Sucher-Feinberg identity serves then to introduce the differential form of the virial theorem in a many-electron system. Following very recent work of Holas and March, this is used to obtain the exact exchange-correlation potential as a path integral expressed in terms of low-order density matrices. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 359-372 
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    Topics: Chemistry and Pharmacology
    Notes: The realization of a Clifford algebra in laboratory space is considered and it is demonstrated that the elements of the algebra cannot, as often assumed, be directly identified with vectors in this space, but, rather, that they form the parametric space of the symmetry operations of the Euclidean group as performed in the laboratory space. Details of this parametrization are established and expressions are given that determine the action of the Euclidean-group operations (screws included) on laboratory-space vectors in terms of the elements of the Clifford algebra. A discussion of Clifford vectors, bivectors, and pseudoscalars and their relation to the Gibbs vectors is provided. The correct definition of axial and polar vectors within the Clifford algebra is carefully discussed. It is shown how simple it is to generate finite point groups in 4-dimensional space by means of the Clifford algebra. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 393-400 
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    Topics: Chemistry and Pharmacology
    Notes: Spin-coupled calculations are carried out for the nitryl halides FNO2 and CINO2. The picture that emerges suggests that the nitrogen atoms use all five valence electrons in covalent bonding. The description of the NO2 group appears to be essentially transferable between the two molecules. No evidence is found for active d-orbital participation in the bonding in either of these molecules or in FPO2. We assess the geometries, charge distributions, and dipole moments of various X3NO and X3PO species (X = H, CH3, or F). We propose a simple rationalization of the dipole moment data without invoking supposed dπ-pπ bonding. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 409-419 
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    Topics: Chemistry and Pharmacology
    Notes: The photoionization cross sections and asymmetry parameters of the three main valence ionization processes in HI, corresponding to the formation of, respectively, 6π, 11σ, and 10σ holes, were calculated in the random-phase approximation (RPA). Our particular computational procedure, based on solving the integral equation for the half on the shell K-matrix upon a grid of points supplied by an L2 basis set calculation, affords recovery of the electronic continuum degeneracy of the final states. This makes it possible to compute the differential ionization cross section at any energy up to the fourth ionization threshold, allowing for the interaction of the three channels considered. The total cross section obtained by applying the Stieltjes imaging procedure to the discrete spectrum yielded by the RPA is also reported. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 453-466 
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    Topics: Chemistry and Pharmacology
    Notes: An extended geminal model has been applied to determine the interatomic potential for the X1Σ+g state Be2. By adopting a [11s, 9p, 6d, 4f, 2g] contracted Gaussian-type basis, the following potential minimum parameters are obtained: Re = 4.67 a.u. (4.63 a.u.) and De = 3.70 mH (3.82 ± 0.05 mH), experimental values in parentheses. A calculation with a nuclei-centered [9s, 7p, 4d, 2f, 1g] GTO basis plus two sets of bond-type function, each set comprising diffuse (2s, 2p, 2d, 2f, 1g) GTOs, yielded -3.79 mH as the value of the potential at R = 4.63 a.u. On the basis of an error analysis the best theoretical estimate of the binding energy is determined to be 3.83 ± 0.08 mH. The calculated value for the fundamental vibrational frequency is v0→1 = 224.7 cm-1 (exp. = 224 ± 3 cm). © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 487-492 
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    Topics: Chemistry and Pharmacology
    Notes: The second electric dipole hyperpolarizability of the lithium atom is calculated using a series of multiconfiguration SCF wave functions with an increasing number of active space orbitals. In agreement with other recent calculations, we find a very large correlation correction to the hyperpolarizability. We analyze the frequency dependence of the dc Kerr hyperpolarizability γK(ο) = γ (- ο ο, 0, 0) and observe very significant dispersion effects. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 505-512 
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    Topics: Chemistry and Pharmacology
    Notes: The S0 and S1 potential energy surfaces of pentalene were studied using MMVB - a hybrid force-field/parametrized valence bond (VB) method designed to simulate CASSCF calculations for ground and covalent excited states. The results were calibrated against full CASSCF calculations. Four distinct critical points were optimized: on S0, a C2h minimum (with alternating single and double bonds) and a D2h transition structure; and on S1, a D2h minimum and an adjacent S1/S0 conical intersection. A VB exchange density matrix (which is independent of the choice of the spin-coupled basis) was used to rationalize the S0 and S1 surface topologies. Craig defined pseudoaromatic molecules to be those with nontotally symmetric electronic ground states. For pentalene, this is true for both CASSCF and MMVB calculations: the CASSCF S0 transition structure is an open-shell B1x singlet, and the VB ground state is dominated by a spin-coupling which transforms as B1g. A C2v minimum and a D2h transition structure were located on the CASSCF S2 potential energy surface. This state cannot be represented by MMVB because of the importance of ionic configurations. The characters of the S1 S2 states of pentalene are shown to be reverse of the S1 and S2 states of benzene. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 579-592 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: Position and momentum space plots are presented for localized molecular orbitals in hydrocarbons, boranes, a carborane, and two octahedral transition metal complexes. The p-space representation proves to be valuable for visualizing such orbitals since it highlights the differences in their character from one molecule to another. Factors influencing the form of the orbitals in p space, including the oscillatory behavior caused by contributions to an orbital from more than one center, are examined in detail. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 609-616 
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    Topics: Chemistry and Pharmacology
    Notes: Coupled Hartree-Fock theory is used to compute and map the current density induced in planar hydrocarbons by an external magnetic field. Results of useful accuracy can be obtained with modest (6-31G**) basis sets by employing a continuous gauge transformation. Maps are presented and discussed for benzene, naphthalene, anthracene, tetracene, pentacene, heptacene, and biphenylene. © 1996 John Wiley & Sons, Inc.
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  • 74
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    International Journal of Quantum Chemistry 60 (1996), S. 617-634 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The group-function theory, as proposed by McWeeny for the study of weak intermolecular interactions and developed by Huzinaga in the context of valence-electron methods, is shown to be applicable to the ab initio study of tunable solid-state laser materials made of defective ionic crystals. The applicability of the theory relies on the existence of local electronic states (to which the demonstrated/potential laser activity is ascribed), which are essentially localized in a small cluster of atoms including the defect and whose electron correlation interactions with the surrounding crystal components are negligible. According to the group-function formalism, it is possible (a) to neglect electron correlation effects beyond the defect cluster and (b) to define a quantum mechanical embedding potential which embodies the rest of the so-called host effects. Computationally, the theory becomes applicable as the embedding potential is approximated through ab initio model potentials (AIMP). The results of AIMP embedded-cluster calculations demonstrate that it is possible to calculate the local structure and spectroscopy of the active defect at an ab initio level, the attainable accuracy being comparable to the usual one in molecular ab initio studies in the gas phase. Also, in this article, we present a systematic study of the local distortions produced upon doping divalent first-series transition-metal ions in rock-salt oxides, MO:Me2+ (M=Mg, Ca, Sr; Me=Sc-Zn) and Tl+ in KMgF3 and KF hosts. This study leads to the calculation of the local structures of the defects in these materials, which have not been measured. The results suggest that the use of the mismatch of the empirical ionic radii of the impurity and the substituted ion in order to predict local distortions in doped ionic crystals is not significant when it is smaller than 0.1 Å, and when it is larger, it should be weighted by a reduction factor depending on the host. For the first-series divalent transition-metal ion impurities, this factor is shown to be 0.15 for SrO, 0.25 for CaO, and around 0.50 for MgO. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 649-655 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using ab initio HF/6-31G** and MP2/6-31G** calculations alternative reactions HC(OH)3 → HCO2H + H2O and HC(OH)3 + H2O → HCO2H + 2H2O are investigated and the results are compared with relevant PM3, HF/3-21G, and HF/6-31G data. Reactant and product complexes as well as transition states are located on corresponding potential energy surfaces. © 1996 John Wiley & Sons, Inc.
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  • 76
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    International Journal of Quantum Chemistry 60 (1996), S. 681-687 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular structure of 21 chromophores of indigoid dyes were studied by an ab initio MP2/6-31 + G*/ /HF/6-31 + G* method. Bond lengths and bond angles were affected by π-electron conjugation. The difference between molecular structures of chromophores and indigoid dyes indicated that benzene rings and five-membered rings in indigoid dyes are structurally important. Absorption maxima of chromophores were successfully calculated by the CI-singles-MP2/6-31 + G* theory. Like indigoid dyes, absorption maxima of the chromophores are affected by the positions of the donor and acceptor groups on the trimethine group. Bathochromic shifts of the absorption maxima were observed with the best donor group of (SINGLE BOND)NH among (SINGLE BOND)NH, (SINGLE BOND)O, and (SINGLE BOND)S groups. Appropriate substitution of longer-chain polymethines brought about chromophoric systems having hypsochromic shifts. From these calculations, the absorption maxima of some indigoid dyes could be explained by their chromophores qualitatively. © 1996 John Wiley & Sons, Inc.
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  • 77
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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  • 78
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    International Journal of Quantum Chemistry 60 (1996), S. 789-789 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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  • 79
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    International Journal of Quantum Chemistry 60 (1996), S. 793-801 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that the conventional concepts based on the use of the HOMO and LUMO are founded on very questionable assumptions. In particular, it is shown both theoretically and computationally that the LUMO of almost all neutral atoms and molecules is a continuum function with energy zero. The LUMO of any SCF calculation is an artifact of the basis-expansion method. A proposal is made for the identification of the pair donor and pair acceptor orbitals which play the true role of the HOMO and LUMO. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 825-832 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The G and F matrices in the molecular vibration problem, the secular matrix in Hückel calculation including some nonneighbor interactions, and the Fock matrices at any stage of iteration in the Pariser-Parr-Pople (PPP) calculations on cis- and trans-butadiene, benzene, and s-triaminobenzene systems have been shown to be factorizable by representing them graphically and then applying the generalized technique of splitting of graphs with n-fold symmetry. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 959-969 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Wiener index is a graphical invariant that has found extensive application in chemistry. We define a generating function, which we call the Wiener polynomial, whose derivative is a q-analog of the Wiener index. We study some of the elementary properties of this polynomial and compute it for some common graphs. We then find a formula for the Wiener polynomial of a dendrimer, a certain highly regular tree of interest to chemists, and show that it is unimodal. Finally, we point out a connection with the Poincaré polynomial of a finite Coxeter group. © 1996 John Wiley & Sons, Inc.
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  • 82
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    International Journal of Quantum Chemistry 60 (1996), S. 971-981 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of π-electron systems confined by impenetrable surfaces is presented. The study results in a nonempirical-based approach to obtain confinement-adapted semiempirical π-Hamiltonians including repulsive terms (PPP or Hubbard). The impenetrable surface confinement of a physical system involves changes in the boundary conditions that the eigenvectors of its differential Hamiltonian operator have to fulfill, while the Hamiltonian itself remains unchanged. However, if this Hamiltonian is written in second quantization language, then confinement only involves changes of the Hamiltonian scalar factors (integrals). Semiempirical Hamiltonian integrals are replaced by parameters; therefore, confinement involves only changes of these parameters. It is shown that confinement changes Coulomb (αi) and exchange (βij), while repulsion (γij) parameters remain unaffected. Next, the influence of confinement upon the electron correlation of (i) π-electron molecular systems, (ii) atoms, and (iii) an electron gas is discussed. The behaviour of the correlation energy vs. the confinement size is found to be different for each type of system. A neat explanation of this variety is given in terms of the Coulomb attractive fields of the systems. Some chemical confinement effects such as an increase in the reactivity of π-electron systems is also outlined. © 1996 John Wiley & Sons, Inc.
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  • 83
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    Topics: Chemistry and Pharmacology
    Notes: The Cl2CO … Cl2 complex was studied using ab initio post-Hartree-Fock theory at the MP2 and MP4 levels and, for comparison, the DFT method with 6-311G(2d), 6-311 + G(2d), and Sadlej's medium-size polarized (MSPBS) basis sets. A potential energy search recovered a planar minimum-energy structure characterized by a bent conformation. For this weakly bound complex, the interaction energy corrected for the basis set superposition error amounted to - 0.88, - 1.09, - 1.43, and - 0.38 kcal/mol at the MP4(SDTQ)/6-311G(2d), MP4(SDTQ)/6-311 + G(2d), MP4(SDTQ)/MSPBS, and DFT(Becke3LYP)/6-311 + G(2d) levels of theory, respectively. Two highly symmetrical forms, linear and T-shaped, correspond to transition-state conformers. The analysis of harmonic vibrational frequencies and potential energy distribution was performed at the MP2 and DFT levels with the 6-311 + G(2d) basis set. © 1996 John Wiley & Sons, Inc.
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  • 84
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    International Journal of Quantum Chemistry 60 (1996), S. 1065-1068 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A discussion is presented for possible diamond-lattice-based structures containing holes that can be filled with metal atoms or ions. To allow the formation of coordinative bonds to the metal, some carbon atoms should be replaced by heteroatoms (with nitrogen preferred, but in some cases oxygen or other heteroatoms may be considered). Two types of holes that may lead to the formation of coordinative bonds are discussed in detail: tetrahedral holes for four such bonds and quasi-octahedral holes for six such bonds. In turn, when suitably arranged in a translationally symmetric manner, these holes may resemble open or closed pores in foams; when they are open, the “channels” may lead to interesting properties with regard to metallic conductivity or superconductivity. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 1081-1091 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electrostatic and hydrophobic complementarities between chymotrypsin and its inhibitor, avian ovomucoid third domains, were evaluated for eight species, which have different amino acid sequences, using molecular electrostatic potential (MEP) and MEP correlation, and the enzyme-inhibitor interaction was analyzed. The changes in the electrostatic and hydrophobic complementarities caused by the amino acid replacements were reflected clearly in the calculated MEP correlation, and it explained the observed binding association constants correctly. The electrostatic complementarity due to arginine at P′3 strongly promotes the binding process of the inhibitor, while the hydrophobic complementarity in the P1 and P′2 positrons also affects the binding process. It was demonstrated that our method is an effective molecular modeling tool in drug design and protein engineering. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 1179-1187 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction between solutes and simple solvents in dilute solutions is analyzed in a systematic way. Different theoretical methods to describe specific solute-solvent interactions and general solvation effects are presented. Finally, the importance of solvent-induced changes in solute properties is discussed through the use of mixed quantum mechanics/classical mechanics strategies. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 743-752 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Secular polynomials (SPs) have been constructed and studied for the adjacency matrices A(GaCh) and A(GbCh) corresponding to chemical graphs of alkanes in terms of atoms (GaCh) and in terms of bonds (GbCh). The three second-class Chebyshev polynomials Up(Q), Up - 1(Q), and Up - 2(Q), with respect to the variable Q proportional to the SP of an isolated CH2-like subgraph, have been shown to appear within both SPs P[A(GaCh)] and P[A(GbCh)] and to play the role of algebraic analogues of a (CH2)p-like subgraph. Common noncanonical algebraic expressions for both SPs reflecting the regular internal structure of alkanes have been constructed on this basis. Spectral properties of both graphs GaCh and GbCh have been shown to be determined by those of Up(Q), e.g., the band limits of spectra proved to be related to the orthogonality interval Q = [-1;1] for polynomials Up(Q). Since the adjacency matrices (AMs) A(GbCh), but not A(GaCh), are proportional to definite model Hamiltonian matrices, the obtained results serve to interpret the one-electron spectra of alkanes in terms of peculiarities of usual chemical structure. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 779-788 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A computational study of substituent effects on methane activation and elimination by high-valent zirconium complexes is reported. Substituent (Z) effects (in a structural, electronic, and enthalpic sense) are substantially less important for the imido (LnZr(DOUBLE BOND)NZ) and imidolike TS than the amido (LnM(SINGLE BOND)NHZ). For the microscopic reverse reaction, methane CH activation, it suggests that tailoring imido reactivity through electronic modification of nitrogen substituents will be difficult. Analysis of the earliest part of the reaction coordinate for methane elimination entails structural deformation of the Zr - amido to assume an appropriate geometry for elimination, which, in some cases, is directly reflected in substantially higher elimination barriers. Lower elimination barriers correlate with stronger agostic bonding, providing further support for the crucial importance of agostic bonding in facilitating alpha-elimination processes for high-valent transition-metal complexes. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 791-791 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
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  • 90
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    International Journal of Quantum Chemistry 60 (1996), S. 821-824 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present a technique to generate Cartesian Gaussian bases for electronic configuration and cross-section calculations on molecules. The technique is specially useful for pseudopotential work, when the bases cannot be tabulated because they depend on the specific choice of the pseudopotential. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 843-852 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some features of the multipole expansion of the Coulomb potential V for a system of point charges are studied. It is shown that multipole expansion is convergent both locally in L2(R3) and weakly on some classes of functions. One-particle Hamiltonians Hn = H0 + Vn, where H0 is the kinetic energy operator and Vn is the n-th partial sum of the multipole expansion of V, are discussed, and the convergence of their eigenvalues to those of H = H0 + V with increasing n is proved. It is also shown that the discrete spectrum eigenfunctions of Hn converge to those of H both in L2(R3) (together with their first and second derivatives) and uniformly on R3. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 853-857 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Based on the charge density functional theory, a simple method is proposed to calculate the parallel electron correlation coefficient, correlation charge, and exchange correlation energy. In contrast to the result in the literature, our analysis reveals that the Fermi hole has its fine structure which is different from the model suggested in the literature. © 1996 John Wiley & Sons, Inc.
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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    Topics: Chemistry and Pharmacology
    Notes: An approximate valence bond (AVB) method was parametrized at a microscopic level for proton transfer and hydroxyanion nucleophilic reactions in enzyme catalytic processes. The method was applied to describe hydrolytic activity of phospholipase A2. The AVB parametrization is based on density functional and conventional ab initio calculations calibrated with respect to experimental data in the gas phase. The method was used as a fast generator of the potential energy function in a quantum-classical molecular dynamics (QCMD) simulations describing atomic motions as well as propagation of the proton wave function in the enzyme active site. The protein environment surrounding the active site and solvent effects are included in the model via electrostatic interactions perturbing the original AVB Hamiltonian. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 60 (1996), S. 1133-1141 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present results of the first molecular dynamics study of a new rigidified 18-crown-6 derivative, recently synthesized by Li and Still. We refer to this new crown as s18c6, which contains a central 18-crown-6 core locked into a D3d configuration by the addition of six exocyclic saturated hydrocarbon rings, two of which also contain a single exocyclic heteroatom (X), peripheral to the central cation binding ring. X can be either a hemiacetal (X = oxygen) or hemithioacetal (X = sulfur). The enhanced rigidity and the exocyclic heteroatoms are thought to be involved in the novel cation binding properties of s18c6 in aqueous solutions; it is more ionophoric than 18c6, and it is selective for Na+ over K+ when X = oxygen but is selective for K+ over Na+ when X = sulfur. In the present communication, we report results for the X = oxygen isomer of s18c6. We use a hybrid quantum mechanical/molecular mechanical (QM/MM) approach to study the solvation properties of the uncomplexed crown in H2O. The QM/MM method described here is based on our previous QM/MM study of K+/18c6 which employs the semiempirical AM1 method for s18c6 and the SPC/E model for H2O. Both AM1 and HF/6-31 + G* optimized geometries give similar results for the gas-phase structure of s18c6. The ab initio results show that s186 has a slightly smaller cavity than 18c6 (5.681 vs. 5.802 Å, respectively) based on the average transannular oxygen-oxygen distances. A 100-ps equilibrium molecular dynamics simulation shows that the s18c6 core remains in a rigid D3d configuration. S18c6 avidly binds two solvent waters, one on either side of the macrocycle plane. The simulation average binding energy per bound water is - 14.8 kcal/mol, which is greater than our previously reported result of - 12.3 kcal/mol for H2O bound by 18c6. Both of the s18c6-bound waters maintain multiple hydrogen bonds to the oxygens of the macrocycle, and there is evidence for involvement of the exocyclic oxygens in this binding. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 58 (1996) 
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    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
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  • 96
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    International Journal of Quantum Chemistry 58 (1996), S. 193-202 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe enhancements to the method of partial retention of diatomic differential overlap (PRDDO). The new method, denoted PRDDO/M, employs a basis set of not quite orthogonal atomic orbitals (NQOAOS) and utilizes sparse matrix techniques to greatly increase the computational efficiency for large molecules. Other modifications, including a complete reparametrization of the method against ab initio STO-3G calculations and implementation of integral screening/damping algorithms, are described. The method is an order of magnitude or more faster than are STO 3G single-point calculations using modern ab initio codes, with little loss in accuracy. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 58 (1996), S. 121-121 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstracts.
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    International Journal of Quantum Chemistry 58 (1996), S. 203-216 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electronic structure and bonding of UF6 and UF6- are studied within a relativistic framework using the MOLFDIR program package. A stronger bonding but more ionic molecule is found if one compares the relativistic with the nonrelativistic results. The first peak in the photoelectron spectrum of Karlsson et al. is assigned to the 12γ8u component of the 4t1u orbital, in agreement with other theoretical and experimental results. Good agreement is found between the experimental and theoretical 5f spectrum UF6-. Some properties, like the dissociation energy and electron affinity, are calculated and the necessity of a fully relativistic framework is shown. The Breit interaction has an effect on the core spinors and the spin-orbit splitting of these spinors but the influence on the valence spectrum is negligible. © 1996 John Wiley & Sons, Inc.
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    International Journal of Quantum Chemistry 58 (1996), S. 217-217 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstracts.
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    International Journal of Quantum Chemistry 58 (1996), S. 219-240 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quantum chemical and molecular modeling computations on large molecular systems are defined for the computational facilities assumed to be available from now to the next 4 years. We considered a few topics which are requiring much attention. The correlation energy is discussed in some detail and we have presented two new functionals, called the J-functional and the K-functional, which make use of Coulomb or exchange-type integrals. In addition, we report new computational results for the Coulomb-Hole-Hartree-Fock approximation. Very brief summaries on new developments in relativistic Dirac-Fock computation and in density functional theory, on the advantages gained by using different basis sets in the same computation, and on the promises of parallel computing conclude the article. © 1996 John Wiley & Sons, Inc.
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