We simulate the resonance Raman spectra of trans-stilbene using a recently developed time-independent method that allows computations of the full two-dimensional spectrum as a function of the incident and scattered frequencies, including both the Franck–Condon and the Herzberg–Teller contributions. The potential energy surfaces (PESs) of the ground and resonant states are described in the harmonic approximation using density functional theory PBE0/6-31+G(d,p) calculations in gas phase and in cyclohexane. The simulated spectra are in good agreement with the experimental data [J. Chem. Phys. 83, 5000 (1985)] measured at four different excitation wavelengths, and allow us to unambiguously assign the main experimental bands. We perform an extensive comparison of the performance of four different vertical or adiabatic models for the PES of the resonant state, dissecting the effects of nuclear displacements and Duschinsky mixings on the spectra.
|Titolo:||Effective Time-Independent Studies on Resonance Raman Spectroscopy of Trans-stilbene including Duschinsky effect|
|Data di pubblicazione:||2013|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1080/00268976.2013.809490|
|Appare nelle tipologie:||1.1 Articolo in rivista|