Oscillator Strengths and Transition Dipole Moments from a Simplified Equation-of-Motion Coupled Cluster Formalism within the Frozen-Pair Approximation

Abstract

In this work, we derive the working equations for the transition density matrices within the equation-of-motion frozen-pair coupled-cluster framework. We focus specifically on the recently developed EOM-fpCCSD and EOM-ptCCSD models and present the corresponding transition dipole moments and oscillator strengths obtained via approximate expressions. This formulation avoids the computational overhead of solving the coupled-cluster $Λ$ equations. Furthermore, we employ a matrix inverse approximation to eliminate the need for explicit calculation of the left EOM eigenvectors. The accuracy of the resulting EOM-fpCCD and EOM-ptCCSD excited-state properties is benchmarked against the linear-response (LR)-CCSD method. Our results demonstrate that the description of excited state properties is improved when using EOM-fpCCSD and EOM-ptCCSD models compared to the standard EOM-CCSD variant.