Work

Improved semiclassical dynamics through adiabatic switching trajectory sampling

Year: 2019

Type: article

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.

Source: The Journal of Chemical Physics

DOI: 10.1063/1.5133144

Authors: Riccardo Conte, Lorenzo Parma, Chiara Aieta, Alessandro Rognoni, Michele Ceotto

Institution: University of Milan

Language: English

Topic: Quantum chaos and dynamical systems

Subfield: Statistical and Nonlinear Physics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: green

Funders: European Commission, Ministero dell’Istruzione, dell’Università e della Ricerca, H2020 European Research Council

Awards: Divide and conquer ab initio semiclassical molecular dynamics for spectroscopic calculations of complex systems, G5510290661, G6560529968