Time Domain Simulation of (Resonance) Raman Spectra of Liquids in the Short Time Approximation.

Abstract

Real-time time-dependent density functional theory (RT-TDDFT) and ab initio molecular dynamics (AIMD) are combined to calculate non-resonant and resonant Raman scattering cross sections of periodic systems, allowing for an explicit quantum mechanical description of condensed phase systems and environmental effects. It is shown that this approach to Raman spectroscopy corresponds to a short time approximation of Heller's time-dependent formalism for the description of Raman scattering. Two ways to calculate the frequency-dependent polarizability in a periodic system are presented: (1) via the modern theory of polarization (Berry phase) and (2) via the velocity representation. Both approaches are found to be equivalent for a system of liquid (S)-methyloxirane with the computational settings used. Resulting non-resonance and resonance Raman spectra from the dynamic AIMD/RT-TDDFT approach are compared to the spectra of one gas phase molecule in the harmonic approximation highlighting finite temperature and solvation effects. Using RT-TDDFT to calculate the full frequency-dependent Placzek-type polarizability within one set of simulations covers the non-resonance, near-resonance, and on-resonance regimes on equal footing, thus allowing the calculation of full Raman excitation profiles.