Journal Article

FZJ-2014-05996

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Perturbational treatment of spin-orbit coupling for generally applicable high-level multi-reference methods

Mai, S. (Corresponding Author) ; Mueller, T.FZJ* ; Plasser, F. ; Marquetand, P. ; Lischka, H. ; González, L.

2014
American Institute of Physics Melville, NY

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Please use a persistent id in citations: http://hdl.handle.net/2128/19012  doi:10.1063/1.4892060

Abstract: An efficient perturbational treatment of spin-orbit coupling within the framework of high-level multireference techniques has been implemented in the most recent version of the COLUMBUS quantum chemistry package, extending the existing fully variational two-component (2c) multi-reference configuration interaction singles and doubles (MRCISD) method. The proposed scheme follows related implementations of quasi-degenerate perturbation theory (QDPT) model space techniques. Our model space is built either from uncontracted, large-scale scalar relativistic MRCISD wavefunctions or based on the scalar-relativistic solutions of the linear-response-theory-based multi-configurational averaged quadratic coupled cluster method (LRT-MRAQCC). The latter approach allows for a consistent, approximatively size-consistent and size-extensive treatment of spin-orbit coupling. The approach is described in detail and compared to a number of related techniques. The inherent accuracy of the QDPT approach is validated by comparing cuts of the potential energy surfaces of acrolein and its S, Se, and Te analoga with the corresponding data obtained from matching fully variational spin-orbit MRCISD calculations. The conceptual availability of approximate analytic gradients with respect to geometrical displacements is an attractive feature of the 2c-QDPT-MRCISD and 2c-QDPT-LRT-MRAQCC methods for structure optimization and ab inito molecular dynamics simulations

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Contributing Institute(s):

1. Jülich Supercomputing Center (JSC)

Research Program(s):

1. 411 - Computational Science and Mathematical Methods (POF2-411) (POF2-411)

Appears in the scientific report 2014

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Database coverage:
; ; Current Contents - Physical, Chemical and Earth Sciences ; IF < 5 ; JCR ; NCBI Molecular Biology Database ; Nationallizenz ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Thomson Reuters Master Journal List ; Web of Science Core Collection

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