Two-component multi-configurational second-order perturbation theory with Kramers restricted complete active space self-consistent field reference function and spin-orbit relativistic effective core potential

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We report the formulation and implementation of KRCASPT2, a two-component multi-configurational second-order perturbation theory based on Kramers restricted complete active space self-consistent field (KRCASSCF) reference function, in the framework of the spin-orbit relativistic effective core potential. The zeroth-order Hamiltonian is defined as the sum of nondiagonal one-electron operators with generalized two-component Fock matrix elements as scalar factors. The Kramers symmetry within the zeroth-order Hamiltonian is maintained via the use of a state-averaged density, allowing a consistent treatment of degenerate states. The explicit expressions are derived for the matrix elements of the zeroth-order Hamiltonian as well as for the perturbation vector. The use of a fully variational reference function and nondiagonal operators in relativistic multi-configurational perturbation theory is reported for the first time. A series of initial calculations are performed on the ionization potential and excitation energies of the atoms of the 6p-block; the results display a significant improvement over those from KRCASSCF, showing a closer agreement with experimental results. Accurate atomic properties of the superheavy elements of the 7p-block are also presented, and the electronic structures of the low-lying excited states are compared with those of their lighter homologues.
Publisher
AMER INST PHYSICS
Issue Date
2014-10
Language
English
Article Type
Article
Keywords

COUPLED-CLUSTER METHOD; CONVERGENT BASIS-SETS; ELECTRONIC-STRUCTURE; MOLECULAR SPINORS; PROGRAM PACKAGE; SCF METHOD; PSEUDOPOTENTIALS; 4-COMPONENT; DIRAC; FORMULATION

Citation

JOURNAL OF CHEMICAL PHYSICS, v.141, no.16

ISSN
0021-9606
DOI
10.1063/1.4898153
URI
http://hdl.handle.net/10203/193922
Appears in Collection
CH-Journal Papers(저널논문)
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