A reduced cost four-component relativistic unitary coupled cluster method for atoms and molecules.

ABSTRACT

We present a four-component relativistic unitary coupled cluster method for atoms and molecules. We have used commutator-based non-perturbative approximation using the "Bernoulli expansion" to derive an approximation to the relativistic unitary coupled cluster method. The performance of the full quadratic unitary coupled-cluster singles and doubles method (qUCCSD), as well as a perturbative approximation variant (UCC3), has been reported for both energies and properties. It can be seen that both methods give results comparable to those of the standard relativistic coupled cluster method. The qUCCSD method shows better agreement with experimental results due to the better inclusion of relaxation effects. The relativistic UCC3 and qUCCSD methods can simulate the spin-forbidden transition with easy access to transition properties. A natural spinor-based scheme to reduce the computational cost of relativistic UCC3 and qUCCSD methods has been discussed.