Theory, implementation, and disappointing results for two-photon absorption cross sections within the doubly electron-attached equation-of-motion coupled-cluster framework

Abstract

The equation-of-motion coupled-cluster singles and doubles method with double electron attachment (EOM-DEA-CCSD) is capable of computing reliable energies, wave functions, and first-order properties of excited states in diradicals and polyenes that have a significant doubly excited character with respect to the ground state, without the need for including the computationally expensive triple excitations. Here, we extend the capabilities of the EOM-DEA-CCSD method to the calculations of a multiphoton property, two-photon absorption (2PA) cross sections. Closed-form expressions for the 2PA cross sections are derived within the expectation-value approach using response wave functions. We analyze the performance of this new implementation by comparing the EOM-DEA-CCSD energies and 2PA cross sections with those computed using the CC3 quadratic response theory approach. As benchmark systems, we consider transitions to the states with doubly excited character in twisted ethene and in polyenes, for which EOM-EE-CCSD (EOM-CCSD for excitation energies) performs poorly. The EOM-DEA-CCSD 2PA cross sections are comparable with the CC3 results for twisted ethene; however, the discrepancies between the two methods are large for hexatriene. The observed trends are explained by configurational analysis of the 2PA channels.