Herzberg–Teller coupling in coherent multidimensional spectroscopy: Analytical response functions for multilevel systems

Abstract

Coherent multidimensional spectroscopy enables detailed investigations of vibronic effects in molecular and solid-state systems. We present explicit analytical expressions for multidimensional nonlinear response functions in the presence of Herzberg–Teller (non-Condon) coupling, within the displaced harmonic oscillator model. The formulation applies to electronic systems with an arbitrary number N of electronic states and to response functions of arbitrary order M in the light–matter interaction. We show that Herzberg–Teller coupling introduces additional oscillatory factors in the time-domain response functions, leading, upon Fourier transformation, to replicas of the Franck–Condon multidimensional spectra shifted by integer multiples of the vibrational frequencies. The present results provide a general analytical framework for the interpretation of non-Condon effects in coherent multidimensional spectroscopies. A Python code that implements the present approach and simulates multidimensional spectra for N-level systems is available on GitHub.