Inspecting molecular aggregate quadratic vibronic coupling effects using squeezed coherent states

Abstract

We present a systematic comparison of three quantum mechanical approaches describing excitation dynamics in molecular complexes using the time-dependent variational principle (TDVP) with increasing sophistication trial wavefunctions (ansatze): Davydov D₂, squeezed D₂ (sqD₂) and a numerically exact multiple D₂ (mD₂) ansatz in order to characterize validity of the sqD₂ ansatz. Numerical simulations of molecular aggregate absorption and fluorescence spectra with intra- and intermolecular vibrational modes, including quadratic electronic–vibrational (vibronic) coupling term, which is due to vibrational frequency shift upon pigment excitation are presented. Simulated absorption and fluorescence spectra of a J type molecular dimer with high frequency intramolecular vibrational modes obtained with D₂ and sqD₂ ansatze match the spectra of mD₂ ansatz only in the single pigment model without quadratic vibronic coupling. In general, the use of mD₂ ansatz is required to model an accurate dimer and larger aggregate's spectra. For a J dimer aggregate coupled to a low frequency intermolecular phonon bath, absorption and fluorescence spectra are qualitatively similar using all three ansatze. The quadratic vibronic coupling term in both absorption and fluorescence spectra manifests itself as a lineshape peak amplitude redistribution, static frequency shift and an additional shift, which is temperature dependent. Overall the squeezed D₂ model does not result in a considerable improvement of the simulation results compared to the simplest Davydov D₂ approach.