Ab Initio Calculations of Polarizabilities Including Relativistic Effects For Elements of Groups IA and IB

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Ohio State University

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The effects of relativity and the concept of core-valence separation have been examined with respect to polarizabilities for elements of groups. IA and IB. The coupled Hartree-Fock method for atomic polarizabilities has been incorporated into an ab initio atomic self-consistent field program. Relativistic effects have been studied via ab initio calculations employing relativistic (REP) and nonrelativistic effective core potentials (NEP). The effects of re-definition of core and valence spaces have been studied by deriving REP's for heavy elements for a set of cases whereby fewer and fewer electrons are ``frozen'' into the core. In addition, core-valence correlation effects have been examined by calculating atomic polarizabilities via a finite-field formalism and configuration interaction calculations. The magnitudes of relativistic and core-valence correlation effects and the impact of definition of core-valence space are compared. The impact of this work on molecular studies employing effective potentials is discussed.


This work was supported through NSF Grant No. CHE-8712315
Author Institution: Department of Chemistry and Chemical Engineering, Stevens Institute of Technology