Analytic energy derivatives for the equation-of-motion coupled-cluster method: Algebraic expressions, implementation and application to theS 1 state of HFCO

Abstract

The general theory of analytic derivatives for the equation-of-motion coupled cluster (EOM-CC) method is reviewed. Special attention is paid to the EOM-CC singles and doubles (EOM-CCSD) approximation, which has the same computational scaling properties as the coupled-cluster singles doubles (CCSD) ground state method and is therefore applicable to a wide range of molecular systems. The detailed spin orbital equations that must be solved in EOM-CCSD gradient calculations are presented for the first time, and some guidelines are discussed regarding their computational implementation. Finally, use of the EOM-CCSD gradient method is illustrated by determining the structure, dipole moment components, harmonic frequencies and infrared intensities of formyl fluoride (HFCO) in its singlet excited (n, π*) state.