We derive a somewhat crude, yet very efficient semiclassical approximation for computing nonadiabatic spectra. The resulting method, which is a generalization of the multiple-surface dephasing representation, includes quantum effects through interference of mixed quantum-classical trajectories and through quantum treatment of the collective electronic degree of freedom. The method requires very little computational effort beyond the fewest-switches surface hopping or Ehrenfest locally mean-field dynamics and is very easy to implement. The proposed approximation is tested by computing the absorption and time-resolved stimulated emission spectra of pyrazine using the four-dimensional three-surface model which allows for comparison with the numerically exact quantum spectra. As expected, the multiple-surface dephasing representation is not suitable for high-resolution linear spectra, yet it seems to capture all the important features of pump-probe spectra. Finally, the method is combined with on-the-fly ab initio evaluation of the electronic structure (i.e., energies, forces, electric-dipole, and nonadiabatic couplings) in order to compute fully dimensional nonadiabatic spectra of pyrazine without approximations inherent to analytical, including vibronic-coupling models. The Appendix provides derivations of perturbative expressions for linear and pump-probe spectra of arbitrary mixed states and for arbitrary laser pulse shapes.
Skip Nav Destination
Article navigation
7 October 2014
Research Article|
October 02 2014
Efficient on-the-fly ab initio semiclassical method for computing time-resolved nonadiabatic electronic spectra with surface hopping or Ehrenfest dynamics
Tomáš Zimmermann;
Tomáš Zimmermann
Laboratory of Theoretical Physical Chemistry, Institut des Sciences et Ingénierie Chimiques,
Ecole Polytechnique Fédérale de Lausanne (EPFL)
, CH-1015 Lausanne, Switzerland
Search for other works by this author on:
Jiří Vaníček
Jiří Vaníček
a)
Laboratory of Theoretical Physical Chemistry, Institut des Sciences et Ingénierie Chimiques,
Ecole Polytechnique Fédérale de Lausanne (EPFL)
, CH-1015 Lausanne, Switzerland
Search for other works by this author on:
a)
Electronic mail: jiri.vanicek@epfl.ch
J. Chem. Phys. 141, 134102 (2014)
Article history
Received:
January 07 2014
Accepted:
September 18 2014
Citation
Tomáš Zimmermann, Jiří Vaníček; Efficient on-the-fly ab initio semiclassical method for computing time-resolved nonadiabatic electronic spectra with surface hopping or Ehrenfest dynamics. J. Chem. Phys. 7 October 2014; 141 (13): 134102. https://doi.org/10.1063/1.4896735
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Pay-Per-View Access
$40.00
Citing articles via
A theory of pitch for the hydrodynamic properties of molecules, helices, and achiral swimmers at low Reynolds number
Anderson D. S. Duraes, J. Daniel Gezelter
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
Electronic structure simulations in the cloud computing environment
Eric J. Bylaska, Ajay Panyala, et al.
Related Content
Measuring nonadiabaticity of molecular quantum dynamics with quantum fidelity and with its efficient semiclassical approximation
J. Chem. Phys. (March 2012)
Evaluation of the importance of spin-orbit couplings in the nonadiabatic quantum dynamics with quantum fidelity and with its efficient “on-the-fly” ab initio semiclassical approximation
J. Chem. Phys. (August 2012)
Ehrenfest dynamics is purity non-preserving: A necessary ingredient for decoherence
J. Chem. Phys. (August 2012)
Coherence penalty functional: A simple method for adding decoherence in Ehrenfest dynamics
J. Chem. Phys. (May 2014)
Ehrenfest and classical path dynamics with decoherence and detailed balance
J. Chem. Phys. (May 2019)