Vibrational response functions for multidimensional electronic spectroscopy: From Duschinsky rotations to multimode squeezed coherent states.

Abstract

Multidimensional spectroscopy unveils the interplay of nuclear and electronic dynamics, which characterizes the ultrafast dynamics of various molecular and solid-state systems. In a class of models widely used for the simulation of such dynamics, field-induced transitions between electronic states result in linear transformations (Duschinsky rotations) between the normal coordinates of the vibrational modes. Here, we present an approach for the calculation of the response functions, based on the explicit derivation of the vibrational state. This can be shown to coincide with a multimode squeezed coherent state, whose expression we derive within a quantum-optical formalism, and specifically by the sequential application to the initial state of rotation, displacement, and squeeze operators. The proposed approach potentially simplifies the numerical derivation of the response functions, avoiding the time integration of the Schrödinger equation, the Hamiltonian diagonalization, and the sum over infinite vibronic pathways. In addition, it quantitatively substantiates in the considered models the intuitive interpretation of the response functions in terms of the vibrational wave packet dynamics.