Improving the accuracy and efficiency of time-resolved electronic spectra calculations: Cellular dephasing representation with a prefactor

Journal Article · Wed Aug 07 00:00:00 EDT 2013 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4817005· OSTI ID:22220483

Zambrano, Eduardo; Šulc, Miroslav; Vaníček, Jiří ^[1]

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1. Laboratory of Theoretical Physical Chemistry, Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne (Switzerland)

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.

• OSTI ID: 22220483
• Journal Information: Journal of Chemical Physics, Vol. 139, Issue 5; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
74 ATOMIC AND MOLECULAR PHYSICS
ACCURACY
CARBON COMPOUNDS
EFFICIENCY
FOURIER TRANSFORMATION
HARMONIC OSCILLATORS
HARMONIC POTENTIAL
NITROGEN COMPOUNDS
ORGANIC COMPOUNDS
OSCILLATORS
PHASE SPACE
SPECTRA
STIMULATED EMISSION
TIME RESOLUTION