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.

submitted

References in corpus (7)

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Cited by in corpus (9)

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• Finite-temperature, anharmonicity, and Duschinsky effects on the two-dimensional electronic spectra from ab initio thermo-field Gaussian wavepacket dynamics
• An Effective Semiclassical Approach to IR Spectroscopy
• Vibrational Investigation of Nucleobases by Means of Divide and Conquer Semiclassical Dynamics
• Quantum to classical transition in the work distribution for chaotic systems
• Semiclassical approach to the work distribution
• Path integral approach to the quantum fidelity amplitude
• Semiclassical evolution of correlations between observables
• Refined approach to cellularization: going from Heller's thawed Gaussian approximation to the Herman--Kluk propagator