Perturbational treatment of spin-orbit coupling for generally applicable high-level multi-reference methods.
作者： Sebastian Mai , Thomas Müller , Felix Plasser , Philipp Marquetand , Hans Lischka
DOI: 10.1063/1.4892060
关键词: Ab initio quantum chemistry methods 、 Chemistry 、 Wave function 、 Coupled cluster 、 Perturbation theory 、 Coupling 、 Potential energy 、 Configuration interaction 、 Scalar (mathematics) 、 Classical mechanics
摘要: An efficient perturbational treatment of spin-orbit coupling within the framework high-level multi-reference techniques has been implemented in most recent version Columbus quantum chemistry package, extending existing fully variational two-component (2c) configuration interaction singles and doubles (MRCISD) method. The proposed scheme follows related implementations quasi-degenerate perturbation theory (QDPT) model space techniques. Our is built either from uncontracted, large-scale scalar relativistic MRCISD wavefunctions or based on scalar-relativistic solutions linear-response-theory-based multi-configurational averaged quadratic coupled cluster method (LRT-MRAQCC). latter approach allows for a consistent, approximatively size-consistent size-extensive coupling. described detail compared to number inherent accuracy QDPT validated by comparing cuts potential energy surfaces acrolein its S, Se, Te analoga with corresponding data obtained matching calculations. conceptual availability approximate analytic gradients respect geometrical displacements an attractive feature 2c-QDPT-MRCISD 2c-QDPT-LRT-MRAQCC methods structure optimization ab inito molecular dynamics simulations.
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