Quasienergy formulation of damped response theory

Abstract

We present a quasienergy-based formulation of damped response theory where a common effective lifetime parameter has been introduced for all excited states in terms of complex excitation energies. The introduction of finite excited state lifetimes leads to a set of (complex) damped response equations, which have the same form to all orders in the perturbation. An algorithm is presented for solving the damped response equations in Hartree-Fock theory and Kohn-Sham density functional theory. The use of the quasienergy formulation allows us to obtain directly the computationally simplest expressions for damped response functions by applying a set of response parameter elimination rules, which minimize the total number of damped response equations to be solved. In standard response theory broadened absorption spectra are obtained by ad hoc superimposing lineshape functions onto the absorption stick spectra, whereas an empirical lineshape function common to all excitations is an integrated part of damped response theory. By superimposing the lineshape functions inherent in damped response theory onto the stick spectra of standard response theory, we show that the absorption spectra obtained in standard and damped response theory calculations are identical. We demonstrate that damped response theory may be applied to obtain absorption spectra in all frequency ranges, also those that are not readily addressed using standard response theory. This makes damped response theory an effective tool, e.g., for determining absorption spectra for large molecules, where the density of the excited states may be very high, and where standard response theory therefore is not applicable in practice. A thorough comparison is given between our formulation of damped response theory and the formulation by Norman et al. [J. Chem. Phys. 123, 194103 (2005)].