Cumulant expansion for fast estimate of non-Condon effects in vibronic transition profiles
Abstract When existing, cumulants can provide valuable information about a given distribution and can in principle be used to either fully reconstruct or approximate the parent distribution function. A previously reported cumulant expansion approach for Franck–Condon profiles [Faraday Discuss., 150,...
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| Auteurs principaux: | , |
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| Format: | article |
| Langue: | EN |
| Publié: |
Nature Portfolio
2017
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| Accès en ligne: | https://doaj.org/article/db9a25141ff64723b7ed23f0ab227e88 |
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| Résumé: | Abstract When existing, cumulants can provide valuable information about a given distribution and can in principle be used to either fully reconstruct or approximate the parent distribution function. A previously reported cumulant expansion approach for Franck–Condon profiles [Faraday Discuss., 150, 363 (2011)] is extended to describe also the profiles of vibronic transitions that are weakly allowed or forbidden in the Franck–Condon approximation (non-Condon profiles). In the harmonic approximation the cumulants of the vibronic profile can be evaluated analytically and numerically with a coherent state-based generating function that accounts for the Duschinsky effect. As illustration, the one-photon 1 1Ag → 1 1B2u UV absorption profile of benzene in the electric dipole and (linear) Herzberg–Teller approximation is presented herein for zero Kelvin and finite temperatures. |
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