6533b85bfe1ef96bd12ba11a

RESEARCH PRODUCT

Perturbative treatment of spin-orbit-coupling within spin-free exact two-component theory using equation-of-motion coupled-cluster methods.

subject

description

A scheme is reported for the perturbative calculation of spin-orbit coupling (SOC) within the spin-free exact two-component theory in its one-electron variant (SFX2C-1e) in combination with the equation-of-motion coupled-cluster singles and doubles method. Benchmark calculations of the spin-orbit splittings in 2Π and 2P radicals show that the accurate inclusion of scalar-relativistic effects using the SFX2C-1e scheme extends the applicability of the perturbative treatment of SOC to molecules that contain heavy elements. The contributions from relaxation of the coupled-cluster amplitudes are shown to be relatively small; significant contributions from correlating the inner-core orbitals are observed in calculations involving third-row and heavier elements. The calculation of term energies for the low-lying electronic states of the PtH radical, which serves to exemplify heavy transition-metal containing systems, further demonstrates the quality that can be achieved with the pragmatic approach presented here.