Comparison of simplified sum-over-state expressions to calculate resonance Raman intensities including Franck-Condon and Herzberg-Teller effects

Julien Guthmuller

doi:10.1063/1.4941449

Comparison of simplified sum-over-state expressions to calculate resonance Raman intensities including Franck-Condon and Herzberg-Teller effects

Abstract

Sum-over-state (SOS) expressions to simulate absorption spectroscopy and resonance Raman (RR) scattering including Franck-Condon (FC) and Herzberg-Teller (HT) effects are described. Starting from the general SOS method, several simplified SOS formulae are derived. In particular, within the so-called independent mode displaced harmonic oscillator model, it is shown that including the vibronic structure in the absorption and RR spectra only requires the calculation of FC overlap integrals of the type ⟨θ g0 |θ ev ⟩ θg0|θev , where g, e, and v stand for the electronic ground state, excited state, and vibrational quantum number, respectively. Additionally, an approximation of the latter approach is introduced, referred as the simplified Φe method, in which the FC factors are neglected. This method is advantageous from the computational point of view and it is demonstrated that it reproduces the main characteristics of the more involved approaches. The merits and drawbacks of the different methods are discussed by applying them to the prototypical compound of Rhodamine 6G. Overall, this work intends to unravel and clarify some differences in the SOS theories of RR scattering.

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Julien Guthmuller prof. dr hab.

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DOI:: Digital Object Identifier (open in new tab) 10.1063/1.4941449
License: Copyright (2016 AIP Publishing)

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Category:: Articles
Type:: artykuł w czasopiśmie wyróżnionym w JCR
Published in:: JOURNAL OF CHEMICAL PHYSICS no. 144, edition 6, pages 1 - 13,
ISSN: 0021-9606
Language:: Polish
Publication year:: 2016
Bibliographic description:: Guthmuller J.: Comparison of simplified sum-over-state expressions to calculate resonance Raman intensities including Franck-Condon and Herzberg-Teller effects// JOURNAL OF CHEMICAL PHYSICS. -Vol. 144, iss. 6 (2016), s.1-13
DOI:: Digital Object Identifier (open in new tab) 10.1063/1.4941449
Verified by:: Gdańsk University of Technology