Application of the mixed time-averaging semiclassical initial value representation method to complex molecular spectra

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

Abstract

The recently introduced mixed time-averaging semiclassical initial value representation of the molecular dynamics method for spectroscopic calculations [M. Buchholz, F. Grossmann, and M. Ceotto, J. Chem. Phys. 144, 094102 (2016)] is applied to systems with up to 61 dimensions, ruled by a condensed phase Caldeira-Leggett model potential. By calculating the ground state as well as the first few excited states of the system Morse oscillator, changes of both the harmonic frequency and the anharmonicity are determined. The method faithfully reproduces blueshift and redshift effects and the importance of the counter term, as previously suggested by other methods. Different from previous methods, the present semiclassical method does not take advantage of the specific form of the potential and it can represent a practical tool that opens the route to direct ab initio semiclassical simulation of condensed phase systems. Published by AIP Publishing.

Details

Original languageEnglish
Article number164110
Number of pages11
JournalJournal of Chemical Physics
Volume147
Issue number16
Publication statusPublished - 28 Oct 2017
Peer-reviewedYes

External IDs

Scopus 85032572273

Keywords

Keywords

  • VALUE SERIES REPRESENTATION, THERMAL RATE CONSTANTS, HYBRID APPROACH, PATH-INTEGRALS, PHASE-SPACE, QUANTUM, DYNAMICS, ABSORPTION, SYSTEMS, I-2