Coupled-cluster theories for the polarizable continuum model. II. analytical gradients for excited states of molecular solutes by the equation of motion coupled-cluster method

摘要

The theory for the analytical energy gradients of excited electronic state described by equation of motion couped-cluster method (EOM-CC) (Stanton, J Chem Phys, 1993, 99, 8840) has been generalized to molecules in solution within the polarizable continuum model (PCM) framework (Miertu? et al. Chem Phys 1981, 55, 117). The final equations of the PCM-EOM gradients are developed at the single and double excitation level (CCSD) and are cast in a form similar to that developed for the ground state CC energy derivatives of solvated molecules (Cammi, J Chem Phys 2009, 131, 164104), involving contraction of effective one- and two-particle density matrices with differentiated one- and two-electron integrals over atomic orbitals.