Resonance Raman spectroscopy from ab initio Hagedorn wavepacket dynamics

Abstract

We present a practical, ab initio time-dependent method using Hagedorn wavepackets to simulate resonance Raman (RR) spectra of polyatomic molecules. Hagedorn functions---Gaussians multiplied by specific polynomials---are used to represent RR initial and final states because these functions are exact solutions to the time-dependent Schrödinger equation for at-most-quadratic potentials and can be propagated at zero cost beyond that of propagating the guiding Gaussian. Using efficient recursive formulae to compute overlaps between Hagedorn wavepackets, we can evaluate RR excitation profiles for arbitrary spectral signals, such as fundamental, overtone, combination, and hot bands. We then construct the Stokes and anti-Stokes RR spectra from these profiles. We first validate the method in a two-dimensional displaced, distorted, and Duschinsky-rotated harmonic model against numerically exact split-operator calculations. Then, we apply the method to compute RR spectra of anthracene by performing dynamics on a 66-dimensional harmonic potential energy surface constructed from density functional theory calculations.