Calculation of absorption and resonance Raman cross sections of ClO₂ in the gas‐phase and in solution: including Duschinsky effects

Abstract

The time-correlation function formalism has been used to calculate resonance Raman cross sections, excitation profiles, and electronic absorption spectra of the OClO molecule in the gas-phase and in different solvents like cyclohexane, chloroform, and water. The multidimensional time domain integrals that arise in these calculations have been evaluated for the case in which an X 2 B 1 -Ã 2 A 1 electronic transition takes place between displaced-distorted-rotated harmonic potential energy surfaces. Ab initio calculations have been performed to provide the spectroscopic constants required for the evaluation of these integrals. The calculated absorption spectra and resonance Raman cross sections have been compared with the experimental results.

Recent advances in linear and nonlinear Raman spectroscopy. Part IV

“…Here we highlight three papers whose principal focus is RRS. Dehestani158 has calculated absorption and resonance Raman cross sections of ClO 2 in the gas phase and in solution, including Duschinsky effects. A time‐correlation function formalism was used to calculate resonance Raman cross sections, profiles, and electronic absorption spectra of the OCIO molecule in the gas phase and in different solvents like cyclohexane, chloroform, and water.…”

Effects of Displacement–Distortion of Potential Energy Surfaces on Nonadiabatic Electron Transfers via Conical Intersections: Application to SO2 and trans-1,3,5-Hexatriene

“…The general expressions for multidimensional time-domain integrals that arise in the calculation of absorption and resonance Raman cross sections have been derived with the assumption that the lower and the resonant harmonic potential surfaces are displaced, distorted, and rotated . These expressions derived have been applied for calculation of resonance Raman spectra of trans -stilbene and ClO 2 . The time-correlation function formalism has been applied to include S1–S2 vibronic coupling in trans -1,3,5-hexatriene (THT) and SO 2 .…”

Absorption and resonance Raman spectroscopy of the 1Bu state of trans‐1,3,5‐hexatriene including vibronic coupling

“…[11] We have recently implemented this method, for the first time, to simulate absorption and RR spectra of transstilbene [12] and OClO. [13] Here, we improve the time-correlation function formalism to include S 1 -S 2 vibronic coupling in THT molecule. In this work, we study vibronic coupling on a model that can be solved on the basis of perturbation theory.…”

“…In a previous work, we derived general expressions for the multidimensional time‐domain integrals that arise in the calculation of absorption and RR cross sections as sums of products of Hermite polynomials with the assumption that the lower and the resonant harmonic potential surfaces are displaced, distorted, and rotated 11. We have recently implemented this method, for the first time, to simulate absorption and RR spectra of trans ‐stilbene12 and OClO 13. Here, we improve the time‐correlation function formalism to include S 1 S 2 vibronic coupling in THT molecule.…”

“…are independent of the vibrational levels, so E 0cγ − E 0 bβ = E 0 c − E 0 b ∼ = .This leads to the expressions that are independent of the diabatic vibrational wave functions of the dark electronic state ϕ 0 b [Eqns(13),(16), and…”