Single determinant calculations of excited state polarizabilities

Abstract

We apply response theory to simulate excited state polarizabilities emphasizing the possibility to do so by means of optimization of a ground state single determinant only. The excited state polarizabilities are given by the double residues of the cubic response functions. A set of molecules with varying ground state configurations and properties have been considered: water, ozone, formaldehyde, ethylene, butadiene, cyclobutadiene, pyridine, pyrazine and s-tetrazine. The results have been compared to excited state experiments where available and with linear response calculations of the multi-determinant optimized excited state. It is shown that calculations of excited state polarizabilities based on a ground state optimized single determinant work well for most of the cases investigated. This contention is exemplified by the fact the gas phase value from an electrochromism experiment for the polarizability of the 1 1 B 2 excited state of formaldehyde is better reproduced by ground state cubic response theory than by the corresponding separate state linear response function calculation, and by that the calculations call for an experimental reinvestigation of the excited state polarizabilities of s-tetrazine. A few prerequisites are given: The excited state should be isolated in energy, the ordering of the main contributing states should be reproduced, and the geometric conformation of the excited state in question should not be very different from the ground state geometry. The computational and formal advantages of the approach are discussed.