Spin-orbit coupling of DFT/MRCI wavefunctions: Method, test calculations, and application to thiophene

Authors

  • Martin Kleinschmidt,

    1. GMD Research Center for Information Technology, Scientific Computing and Algorithms Institute (SCAI), Schloss Birlinghoven, 53754 St. Augustin, Germany
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  • Jörg Tatchen,

    1. GMD Research Center for Information Technology, Scientific Computing and Algorithms Institute (SCAI), Schloss Birlinghoven, 53754 St. Augustin, Germany
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  • Christel M. Marian

    Corresponding author
    1. GMD Research Center for Information Technology, Scientific Computing and Algorithms Institute (SCAI), Schloss Birlinghoven, 53754 St. Augustin, Germany
    Current affiliation:
    1. Institute of Theoretical Chemistry, Heinrich-Heine-University, Universitätsstr. 1, 40225 Düsseldorf
    • GMD Research Center for Information Technology, Scientific Computing and Algorithms Institute (SCAI), Schloss Birlinghoven, 53754 St. Augustin, Germany
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Abstract

During the past decade the one-center mean-field approximation has proven to be a very appropriate framework for the accurate description of spin-orbit effects at the correlated all-electron level. Here, a new efficient code, SPOCK, is introduced that calculates spin-orbit matrix elements in the one-center mean-field approximation for multireference CI wave functions. For the first time, the computation of spin-dependent interactions within a Kohn-Sham orbital based CI (DFT/MRCI) scheme1 is made possible. The latter approach is suitable for large scale systems with up to 100–200 valence electrons. Test calculations are performed on well-known diatomic molecules and the thiocarbonyl pyranthione. Spin-orbit matrix elements show good agreement with their Hartree-Fock orbital based counterparts but are obtained at considerably lower expense, thus demonstrating the power of the method. As an application singlet-triplet couplings in thiophene are investigated that are important for the photophysics and photochemistry. Spin-orbit matrix elements between all π → π* excited states are found to be small. Considerably larger spin-orbit matrix elements are observed only for cases in which π → σ* excited configurations are involved. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 824–833, 2002

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