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Duschinsky, Herzberg–Teller, and Multiple Electronic Resonance Interferential Effects in Resonance Raman Spectra and Excitation Profiles. The Case of Pyrene
journal contribution
posted on 2013-08-13, 00:00 authored by Francisco
J. Avila Ferrer, Vincenzo Barone, Chiara Cappelli, Fabrizio SantoroWe show that a recently developed
time-independent approach for
the calculation of vibrational resonance Raman (vRR) spectra is able
to describe Duschinsky and Herzberg–Teller (HT) effects acting
on a single resonant state, together with interferential contributions
arising from multiple electronic resonances, allowing us to investigate
in detail how their interplay determines both the vRR spectra at selected
wavelengths and the Raman excitation profiles. We apply this methodology
to the study of the spectra of pyrene in acetonitrile, an ideal system
since it exhibits three close-lying electronic transitions that are
bright but also subjected to HT effects. To single out the different
contributions to vRR line shapes we adopted two different adiabatic
models for resonant-state potential energy surfaces, namely, Adiabatic
Shift (only accounting from equilibrium geometry displacements) and
Adiabatic Hessian (AH, including also the Duschinsky effects), and
Franck–Condon (FC) or HT approximations for the transition
dipole. We show that, on balance, FC+HT calculations within the AH
model provide the best agreement with experiment. Moreover, our methodology
permits to individuate bands in the experimental spectra due to the
simultaneous contribution of more than one resonant state and to point
out and analyze interferential effects between the FC and HT terms
in each resonance Raman process, together with FC-HT and HT-HT interferences
between different electronic states.
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Keywords
HT effectsPyreneWe showinterferential effectsHT termsAdiabatic ShiftHT approximationsvibrational resonance Ramaninterferential contributionsresonance Raman processtransitionvRR spectraFCvRR line shapesHerzbergExcitation ProfilesDuschinskyadiabatic modelsRaman excitation profilesAH modelMultiple Electronic Resonance Interferential EffectscalculationResonance Raman Spectramethodologyenergy surfacesequilibrium geometry displacements
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