Quasi-classical simulations of resonance Raman spectra based on path integral linearization

Based on a linearization approximation coupled with path integral formalism, we propose a method derived from the propagation of quasi-classical trajectories to simulate resonance Raman spectra. This method is based on a ground state sampling followed by an ensemble of trajectories on the mean surface between the ground and excited states. The method was tested on three models and compared to quantum mechanics solution based on a sum-over-states approach: harmonic and anharmonic oscillators and the HOCl molecule (hypochlorous acid). The method proposed is able to correctly characterize resonance Raman scattering and enhancement, including the description of overtones and combination bands. The absorption spectrum is obtained at the same time and the vibrational fine structure can be reproduced for long excited state relaxation times. The method can be applied also to dissociating excited states (as is the case for HOCl).

Automated summary

Based on a linearization approximation and path integral formalism, this study proposes a method to simulate resonance Raman spectra by propagating quasi-classical trajectories. The method involves sampling the ground state and ensemble of trajectories on the mean surface between the ground and excited states. The method was tested on various models and compared to quantum mechanics solution, demonstrating its ability to accurately characterize resonance Raman scattering and enhancement.