We report an explicitly time-dependent coupled-cluster approach to compute linear absorption spectra for molecular systems. The framework is based on the equation-of-motion formalism and the time-evolution of a coupled-cluster dipole function, rather than the coupled-cluster wave function itself. The dipole function formalism introduces no approximations and requires the time-evolution of a single time-dependent object: either the right or the left dipole function. The formalism can be applied to the computation of linear absorption spectra for molecules with a high density-of-states over a broad spectral range, a case for which conventional frequency-domain computations may become impractical. The method is validated by comparing absorption spectra for small molecules obtained from both frequency- and time-domain variants of the equation-of-motion second-order approximate coupled-cluster (EOM-CC2) method. We also perform time-dependent EOM-CC2 computations to predict the extreme ultraviolet absorption spectra for third-row ions. The simulated spectra is shown to be in good agreement with experiment.

Linear absorption spectra from explicitly time-dependent equation-of-motion coupled-cluster theory

253rd National Meeting (2017)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.