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

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.

Vibrational response functions for multidimensional electronic spectroscopy in the adiabatic regime: A coherent-state approach.

Multi-dimensional spectroscopy represents a particularly insightful tool for investigating the interplay of nuclear and electronic dynamics, which plays an important role in a number of photophysical processes and photochemical reactions. Here, we present a coherent state representation of the vibronic dynamics and of the resulting response functions for the widely used linearly displaced harmonic oscillator model. Analytical expressions are initially derived for the case of third-order response functions in an N-level system, with ground state initialization of the oscillator (zero-temperature limit).