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. Besides, it quantitatively substantiates in the considered models the intuitive interpretation of the response functions in terms of the vibrational wave packet dynamics.

References in corpus (5)

• Watching the coherent birth of polaron pairs in conjugated polymers
• Vibrational wave packet induced oscillations in two-dimensional electronic spectra. II. Theory
• Effects of Herzberg--Teller vibronic coupling on coherent excitation energy transfer
• Ultrafast dynamics of photoinduced charge separation
• Simulation of emission spectra of transition-metal dichalcogenide monolayers with the multimode Brownian oscillator model