Vibronic coupling

Vibronic coupling (also called nonadiabatic coupling or derivative coupling) in a molecule involves the interaction between electronic and nuclear vibrational motion.^[1]^[2] The term "vibronic" originates from the combination of the terms "vibrational" and "electronic", denoting the idea that in a molecule, vibrational and electronic interactions are interrelated and influence each other. The magnitude of vibronic coupling reflects the degree of such interrelation.

In theoretical chemistry, the vibronic coupling is neglected within the Born–Oppenheimer approximation. Vibronic couplings are crucial to the understanding of nonadiabatic processes, especially near points of conical intersections.^[3]^[4] The direct calculation of vibronic couplings used to be uncommon due to difficulties associated with its evaluation, but has recently gained popularity due to increased interest in the quantitative prediction of internal conversion rates, as well as the development of cheap but rigorous ways to analytically calculate the vibronic couplings, especially at the TDDFT level.^[5]^[6]^[7]

^ Yarkony, David R (1998). "Nonadiabatic Derivative Couplings". In Paul von Ragué Schleyer; et al. (eds.). Encyclopedia of Computational Chemistry. Chichester: Wiley. doi:10.1002/0470845015.cna007. ISBN 978-0-471-96588-6.
^ Azumi, T. (1977). "What Does the Term "Vibronic Coupling" Mean?". Photochemistry and Photobiology. 25 (3): 315–326. doi:10.1111/j.1751-1097.1977.tb06918.x.
^ Yarkony, David R. (11 January 2012). "Nonadiabatic Quantum Chemistry—Past, Present, and Future". Chemical Reviews. 112 (1): 481–498. doi:10.1021/cr2001299. PMID 22050109.
^ Baer, Michael (2006). Beyond Born-Oppenheimer : electronic non-adiabatic coupling terms and conical intersections. Hoboken, N.J.: Wiley. ISBN 978-0471778912.
^ Wang, Zikuan; Wu, Chenyu; Liu, Wenjian (2021). "NAC-TDDFT: Time-Dependent Density Functional Theory for Nonadiabatic Couplings". Accounts of Chemical Research. 54 (17): 3288–3297. arXiv:2105.10804. doi:10.1021/acs.accounts.1c00312. PMID 34448566. S2CID 235166492.
^ Li, Zhendong; Liu, Wenjian (2014). "First-order nonadiabatic coupling matrix elements between excited states: A Lagrangian formulation at the CIS, RPA, TD-HF, and TD-DFT levels". The Journal of Chemical Physics. 141 (1): 014110. Bibcode:2014JChPh.141a4110L. doi:10.1063/1.4885817. PMID 25005280.
^ Li, Zhendong; Suo, Bingbing; Liu, Wenjian (2014). "First order nonadiabatic coupling matrix elements between excited states: Implementation and application at the TD-DFT and pp-TDA levels". The Journal of Chemical Physics. 141 (24): 244105. Bibcode:2014JChPh.141x4105L. doi:10.1063/1.4903986. PMID 25554131.

[encyclopedia-1] Yarkony, David R (1998). "Nonadiabatic Derivative Couplings". In Paul von Ragué Schleyer; et al. (eds.). Encyclopedia of Computational Chemistry. Chichester: Wiley. doi:10.1002/0470845015.cna007. ISBN 978-0-471-96588-6.

[2] Azumi, T. (1977). "What Does the Term "Vibronic Coupling" Mean?". Photochemistry and Photobiology. 25 (3): 315–326. doi:10.1111/j.1751-1097.1977.tb06918.x.

[3] Yarkony, David R. (11 January 2012). "Nonadiabatic Quantum Chemistry—Past, Present, and Future". Chemical Reviews. 112 (1): 481–498. doi:10.1021/cr2001299. PMID 22050109.

[4] Baer, Michael (2006). Beyond Born-Oppenheimer : electronic non-adiabatic coupling terms and conical intersections. Hoboken, N.J.: Wiley. ISBN 978-0471778912.

[Wang_NAC_review-5] Wang, Zikuan; Wu, Chenyu; Liu, Wenjian (2021). "NAC-TDDFT: Time-Dependent Density Functional Theory for Nonadiabatic Couplings". Accounts of Chemical Research. 54 (17): 3288–3297. arXiv:2105.10804. doi:10.1021/acs.accounts.1c00312. PMID 34448566. S2CID 235166492.

[Li_NAC_theory-6] Li, Zhendong; Liu, Wenjian (2014). "First-order nonadiabatic coupling matrix elements between excited states: A Lagrangian formulation at the CIS, RPA, TD-HF, and TD-DFT levels". The Journal of Chemical Physics. 141 (1): 014110. Bibcode:2014JChPh.141a4110L. doi:10.1063/1.4885817. PMID 25005280.

[Li_NAC_benchmark-7] Li, Zhendong; Suo, Bingbing; Liu, Wenjian (2014). "First order nonadiabatic coupling matrix elements between excited states: Implementation and application at the TD-DFT and pp-TDA levels". The Journal of Chemical Physics. 141 (24): 244105. Bibcode:2014JChPh.141x4105L. doi:10.1063/1.4903986. PMID 25554131.

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