Theory of coherent two-dimensional vibrational spectroscopy

J Chem Phys. 2019 Mar 14;150(10):100901. doi: 10.1063/1.5083966.

Abstract

Two-dimensional (2D) vibrational spectroscopy has emerged as one of the most important experimental techniques useful to study the molecular structure and dynamics in condensed phases. Theory and computation have also played essential and integral roles in its development through the nonlinear optical response theory and computational methods such as molecular dynamics (MD) simulations and electronic structure calculations. In this article, we present the fundamental theory of coherent 2D vibrational spectroscopy and describe computational approaches to simulate the 2D vibrational spectra. The classical approximation to the quantum mechanical nonlinear response function is invoked from the outset. It is shown that the third-order response function can be evaluated in that classical limit by using equilibrium or non-equilibrium MD simulation trajectories. Another simulation method is based on the assumptions that the molecular vibrations can still be described quantum mechanically and that the relevant molecular response functions are evaluated by the numerical integration of the Schrödinger equation. A few application examples are presented to help the researchers in this and related areas to understand the fundamental principles and to use these methods for their studies with 2D vibrational spectroscopic techniques. In summary, this exposition provides an overview of current theoretical efforts to understand the 2D vibrational spectra and an outlook for future developments.