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Improved semiclassical dynamics through adiabatic switching trajectory sampling

Chemical Physics 2019-12-09 v1 Quantum Physics

Abstract

We introduce an improved semiclassical dynamics approach to quantum vibrational spectroscopy. In this method, a harmonic-based phase space sampling is preliminarily driven toward non-harmonic quantization by slowly switching on the actual potential. The new coordinates and momenta serve as initial conditions for the semiclassical dynamics calculation, leading to a substantial decrease in the number of chaotic trajectories to deal with. Applications are presented for model and molecular systems of increasing dimensionality characterized by moderate or high chaoticity. They include a bidimensional Henon-Heiles potential, water, formaldehyde, and methane.The method improves accuracy and precision of semiclassical results and it can be easily interfaced with all pre-existing semiclassical theories.

Keywords

Cite

@article{arxiv.1912.03034,
  title  = {Improved semiclassical dynamics through adiabatic switching trajectory sampling},
  author = {Riccardo Conte and Lorenzo Parma and Chiara Aieta and Alessandro Rognoni and Michele Ceotto},
  journal= {arXiv preprint arXiv:1912.03034},
  year   = {2019}
}
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