Improving the accuracy and efficiency of time-resolved electronic spectra calculations: Cellular dephasing representation with a prefactor
Abstract
Time-resolved electronic spectra can be obtained as the Fourier transform of a special type of time correlation function known as fidelity amplitude, which, in turn, can be evaluated approximately and efficiently with the dephasing representation. Here we improve both the accuracy of this approximation—with an amplitude correction derived from the phase-space propagator—and its efficiency—with an improved cellular scheme employing inverse Weierstrass transform and optimal scaling of the cell size. We demonstrate the advantages of the new methodology by computing dispersed time-resolved stimulated emission spectra in the harmonic potential, pyrazine, and the NCO molecule. In contrast, we show that in strongly chaotic systems such as the quartic oscillator the original dephasing representation is more appropriate than either the cellular or prefactor-corrected methods.
- Publication:
-
Journal of Chemical Physics
- Pub Date:
- August 2013
- DOI:
- 10.1063/1.4817005
- arXiv:
- arXiv:1306.0721
- Bibcode:
- 2013JChPh.139e4109Z
- Keywords:
-
- carbon compounds;
- chaos;
- Fourier transform spectra;
- harmonic oscillators;
- nitrogen compounds;
- organic compounds;
- stimulated emission;
- time resolved spectra;
- 33.20.-t;
- 33.80.Be;
- 02.30.Nw;
- 03.65.Ge;
- 05.45.Mt;
- Molecular spectra;
- Level crossing and optical pumping;
- Fourier analysis;
- Solutions of wave equations: bound states;
- Quantum chaos;
- semiclassical methods;
- Physics - Chemical Physics;
- Quantum Physics
- E-Print:
- submitted