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.
Application of the mixed time-averaging semiclassical initial value representation method to complex molecular spectra / M. Buchholz, F. Grossmann, M. Ceotto. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 147:16(2017 Oct 26), pp. 164110.1-164110.11.
|Titolo:||Application of the mixed time-averaging semiclassical initial value representation method to complex molecular spectra|
BUCHHOLZ, MAX (Primo)
CEOTTO, MICHELE (Corresponding)
|Parole Chiave:||semiclassical molecular dynamics,;Caldeira-Leggett; spectroscopy|
|Settore Scientifico Disciplinare:||Settore CHIM/02 - Chimica Fisica|
|Progetto:||Divide and Conquer ad initio semiclassical molecular dynamics for spectropic calculations of complex systems (SEMICOMPLEX)|
|Data di pubblicazione:||26-ott-2017|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1063/1.4998510|
|Appare nelle tipologie:||01 - Articolo su periodico|