Treatment of Herzberg-Teller and non-Condon effects in optical spectra with Hierarchical Equations of Motion

Abstract: We derive a Hierarchical Equations of Motion (HEOM) description of nonadiabatic Herzberg-Teller type coupling effects and of non-Condon effects in a system of electronic transitions interacting with intra- and inter-molecular vibrational modes. We point out analogies between the auxiliary density operators (ADOs) of the hierarchy and the terms arising from explicit description of the vibrational modes in the Hamiltonian. In comparison with the standard formulation of HEOM, our equations contain additional connections between ADOs in the hierarchy scheme, which account for the dependence of the nonadiabatic coupling elements on the vibrational coordinates. We compare absorption spectra calculated with our HEOM methodology and with explicit treatment of vibrational DOF for a dimer system in the strong resonance coupling regime. Furthermore, we show that for sufficiently strong excitonic coupling, the corresponding effects in linear absorption spectra of vibronic dimers can be captured very well by the concept of effective Huang-Rhys factors.