Spin-Free Exact Two-Component Linear Response Coupled Cluster Theory for the Estimation of Frequency-Dependent Second-Order Properties.

Abstract

We have presented the theory, implementation, and benchmark results for the one-electronic variant of spin-free exact two-component (SFX2C1e) linear response coupled cluster (LRCCSD) theory for static and dynamic polarizabilities of atoms and molecules in the spin-summed formulation. The resolution of identity (RI) approximation for two-electron integrals has been used to reduce the computational cost of the calculation and has been shown to have a negligible effect on accuracy. The calculated static and dynamic polarizability values agree very well with the more expensive X2C-LRCCSD and the experimental results. Our calculated results show that accurate predictions of polarizabilities of atoms and molecules containing heavy atoms require the use of a large basis set containing an adequate number of diffuse functions, in addition to accounting for electron correlation and relativistic effects.