Observatorio de I+D+i UPM

Memorias de investigación
Research Publications in journals:
Relation of exact gaussian basis methods to the dephasing representation: theory and application to time-resolved electronic spectra
Year:2013
Research Areas
  • Physics chemical and mathematical
Information
Abstract
We recently showed that the dephasing representation (DR) provides an efficient tool for computing ultrafast electronic spectra and that further acceleration is possible with cellularization [M. ?ulc and J. Vaní?ek, Mol. Phys.110, 945 (Year: 2012)]10.1080/00268976.2012.668971. Here, we focus on increasing the accuracy of this approximation by first implementing an exact Gaussian basis method, which benefits from the accuracy of quantum dynamics and efficiency of classical dynamics. Starting from this exact method, the DR is derived together with ten other methods for computing time-resolved spectra with intermediate accuracy and efficiency. These methods include the Gaussian DR, an exact generalization of the DR, in which trajectories are replaced by communicating frozen Gaussian basis functions evolving classically with an average Hamiltonian. The newly obtained methods are tested numerically on time correlation functions and time-resolved stimulated emission spectra in the harmonic potential, pyrazine S 0/S 1 model, and quartic oscillator. Numerical results confirm that both the Gaussian basis method and the Gaussian DR increase the accuracy of the DR. Surprisingly, in chaotic systems the Gaussian DR can outperform the presumably more accurate Gaussian basis method, in which the two bases are evolved separately.
International
Si
JCR
No
Title
The Journal of Chemical Physics
ISBN
0021-9606
Impact factor JCR
Impact info
Volume
139
Journal number
From page
034112
To page
034118
Month
SIN MES
Ranking
Participants
  • Autor: Miroslav Sulc (EPFL)
  • Autor: María del Henar Hernández Mendiola (UPM)
  • Autor: T. J. Martínez (EPFL)
  • Autor: Jiri Vanicek (EPFL)
Research Group, Departaments and Institutes related
  • Creador: Departamento: Física y Mecánica Fundamentales y Aplicada a la Ingeniería Agroforestal
S2i 2019 Observatorio de investigación @ UPM con la colaboración del Consejo Social UPM
Cofinanciación del MINECO en el marco del Programa INNCIDE 2011 (OTR-2011-0236)
Cofinanciación del MINECO en el marco del Programa INNPACTO (IPT-020000-2010-22)