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KPACK: Relativistic Two-component Ab Initio Electronic Structure Program Package

  • Kim, Inkoo (Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST)) ;
  • Lee, Yoon Sup (Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST))
  • Received : 2012.10.09
  • Accepted : 2012.10.28
  • Published : 2013.01.20

Abstract

We describe newly developed software named KPACK for relativistic electronic structure computation of molecules containing heavy elements that enables the two-component ab initio calculations in Kramers restricted and unrestricted formalisms in the framework of the relativistic effective core potential (RECP). The spin-orbit coupling as relativistic effect enters into the calculation at the Hartree-Fock (HF) stage and hence, is treated in a variational manner to generate two-component molecular spinors as one-electron wavefunctions for use in the correlated methods. As correlated methods, KPACK currently provides the two-component second-order M${\o}$ller-Plesset perturbation theory (MP2), configuration interaction (CI) and complete-active-space self-consistent field (CASSCF) methods. Test calculations were performed for the ground states of group-14 elements, for which the spin-orbit coupling greatly influences the determination of term symbols. A categorization of three procedures is suggested for the two-component methods on the basis of spin-orbit coupling manifested in the HF level.

Acknowledgement

Supported by : National Research Foundation

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