Nine-dimensional quantum molecular dynamics simulation of intramolecular vibrational energy redistribution in the CHD3 molecule with the help of coupled coherent states

Abstract

A previously developed method of coupled coherent states (CCS) is applied to the simulation of intramolecular vibrational energy redistribution in the CHD3 molecule. All nine modes are taken into account within a fully quantum approach. Emphasis is placed on convergence with respect to the number of coherent states in relation to the desired propagation time, which was taken to be sufficient to resolve Fermi resonance splitting of ∼100 cm−1 at an excitation energy of ∼16 000 cm−1. Fermi-resonance beatings of energy between C–H stretch and two C–H bends as well as slow energy flow to the rest of the molecule are reproduced. Due to the use of Monte Carlo grids the CCS technique scales extremely well with the number of modes and allows fully quantum molecular dynamics simulations of polyatomic systems.