Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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A Relativistiv Configuration Interaction Method Using Effective Core Potentials with Spin-Orbit Interactions

  • Published : 1995.06.20
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Abstract

As an extension to the Kramers' restricted Hartree-Fock (KRHF) method [J. Comp. Chem., 13, 595 (1992)], we have implemented the Kramers' restricted configuration interaction (KRCI) program in order to calculate excited states as well as the ground state of polyatomic molecules containing heavy atoms. This KRCI is based on determinants composed of the two-component molecular spinors which are generated from KRHF calculations. The Hamiltonian employed in the KRHF and KRCI methods contains most of all the important relativistic effects including spin-orbit terms through the use of relativistic effective core potentials (REP). The present program which is limited to a small configuration space has been tested for a few atoms and molecules. Excitation energies of the group 14 and 16 elements calculated using the present KRCI program are in good accordance with the spectroscopic data. Calculated excitation energies for many Rydberg states of K and Cs indicate that spin-orbit terms in the REP, which are derived for the ground state, are also reliable for the description of highly excited states. The electronic states of the polyatomic molecule CH3I are probed from the molecular region to the dissociation limit. Test calculations demonstrate that the present KRCI is a useful method for the description of potential energy surface of polyatomic molecules containing heavy atoms.

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