1306.0721 (Eduardo Zambrano et al.)

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

Eduardo Zambrano, Miroslav Sulc, Jiri Vanicek

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.

View original: http://arxiv.org/abs/1306.0721