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Space Self-consistent Field (space + self-consistent_field)

Distribution by Scientific Domains
Chemistry100%

Kinds of Space Self-consistent Field

  • active space self-consistent field
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  • complete active space self-consistent field
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    Selected Abstracts

    Absorption, resonance, and near-resonance Raman studies of the tetracyanoquinodimethane neutral and its monoanion in terms of density functional theory and complete active space self-consistent field methods

    INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 8 2006
    Marcin Makowski
    Abstract The electronic structure of the 11B1u and 12B3u excited electronic states of the tetracyanoquinodimethane (TCNQ) neutral and its charged derivative are studied within the framework of complete active space self-consistent field (CASSCF) and Becke's three-parameter hybrid method with Lee,Yang,Parr correlation functional (B3LYP) methods applied to the level aug-cc-p-VDZ basis set. Both CASSCF/aug-cc-p-VDZ and B3LYP/aug-cc-p-VDZ treatments provide the ground-state and the excited state geometries; these are then used to assess the Franck,Condon (FC) parameters in the 11B1u state of the neutral TCNQ and in the 12B3u state of the TCNQ monoanion. The quality of numerical results is then tested on the base of available experimental near-resonance and resonance Raman data. The studies are performed in terms of the vibronic model, which takes both FC and mode-mixing (Dushinsky) effects into account. This somewhat simplified vibronic model leads to very good agreement between the theory and the Raman experiments concerning both neutral TCNQ and its monoanion. In particular, the calculated excitation profiles of the ,2 = 2215 cm,1, ,4 = 1389 cm,1, ,5 = 1195 cm,1, and ,9 = 336 cm,1 fundamentals are shown to be in excellent agreement with those for the TCNQ monoanion. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source]

    CASSCF study into the mechanism for predissociation of the allyl radical

    INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2006
    Milena Shahu
    Abstract A theoretical study has been carried out on the allyl radical in its ground and first excited electronic states. Complete active space self-consistent field (CASSCF) calculations show the presence of a conical intersection between the ground and first excited electronic states (,400 cm,1 above the adiabatic excited state energy), reached by decreasing the CCC angle and twisting the CC bonds. The presence of this conical intersection provides a likely explanation for the very rapid predissociation in the excited electronic state. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source]

    Using 1,3-butadiene and 1,3,5-hexatriene to model the cis-trans isomerization of retinal, the chromophore in the visual pigment rhodopsin

    INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4-5 2002
    Fredrik Blomgren
    Abstract The short polyenes 1,3-butadiene and 1,3,5-hexatriene are used to model the cis-trans isomerization of the protonated Schiff base of retinal (PSBR) in rhodopsin (Rh). We employed the complete active space self-consistent field (CASSCF) method for calculation of the potential energy surfaces (PESs) in C2 symmetry. In the calculations, the central bond was twisted from 0 to 180° in the first singly excited singlet state (Sse), i.e., the state dominated by a configuration with one electron excited from HOMO to LUMO. It was found that the PES of 1,3-butadiene has a maximum whereas the PES of 1,3,5-hexatriene has a minimum for a twist angle of 90°. This is explained by a shift in border of single and double bonds in the Sse state. The first step in the cis-trans isomerization of PSBR, which is the formation of the C6C7 (see Scheme 1 for numbering) twisted PSBR in the first excited singlet state (S1), inside the protein binding pocket of the visual pigment Rh is modeled using crystal coordinates and the calculations performed on 1,3-butadiene and 1,3,5-hexatriene. More specifically, a plausible approximate structure is calculated in a geometric way for the C6C7 90° twisted PSBR, which fits into the protein binding pocket in the best possible way. It has been shown earlier that PSBR has an energy minimum for this angle in S1. The CASSCF method was used to investigate the wave function of the calculated structure of PSBR. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 [source]

    Ab initio study on the photochemical behavior of styrene

    JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 10 2002
    Yoshiaki Amatatsu
    Abstract Ab initio complete active space self-consistent field (CASSCF) and the second order multireference Møller-Plesset calculations have been performed to examine the photochemical behavior of styrene upon the strong S0 -S2 electronic excitation in the low-lying excited states. The optimized structure at the S2/S1 conical intersection (CIX) is characterized by a quinoid structure. The transition state (TS) in S1 is in the vicinity of the S2/S1 -CIX. At the S1 -TS, two reaction paths branch. One is the relaxation into the stable structure in S1 and then emission into S0. The other is the radiationless decay through the S1/S0 -CIX. © 2002 Wiley Periodicals, Inc. J Comput Chem 10: 950,956, 2002 [source]