Analytic evaluation of energy first derivatives for spin–orbit coupled-cluster singles and doubles augmented with noniterative triples method: General formulation and an implementation for first-order properties
- 12 February 2021
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 154 (6), 064110
- https://doi.org/10.1063/5.0038779
Abstract
A formulation of analytic energy first derivatives for the coupled-cluster singles and doubles augmented with noniterative triples [CCSD(T)] method with spin–orbit coupling included at the orbital level and an implementation for evaluation of first-order properties are reported. The standard density-matrix formulation for analytic CC gradient theory adapted to complex algebra has been used. The orbital-relaxation contributions from frozen core, occupied, virtual, and frozen virtual orbitals to analytic spin-orbit CCSD(T) gradients are fully taken into account and treated efficiently, which is of importance to calculations of heavy elements. Benchmark calculations of first-order properties including dipole moments and electric-field gradients using the corresponding exact two-component property integrals are presented for heavy-element containing molecules to demonstrate the applicability and usefulness of the present analytic scheme.Funding Information
- U.S. Department of Energy (DE-SC0020317)
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