The Role of Electron-Nuclear Coupling on Chemical and Physical Processes

Abstract:Over the last few decades, Born-Oppenheimer (BO) and Born-Oppenheimer-Huang (BOH) treatments for electron-nuclear equation of motion have been considered as the cornerstone for qualitative as well as quantitative exploration and understanding of chemical and physical processes. The BO approximation due to the large mass difference between electrons and nuclei as well as the energy separation among the electronic states could able to predict some of the processes (chemical and physical) satisfactorily at lower energy regime. Such approximation (BO) quite often fails for those cases with the involvement of excited electronic states, in particular, due to the coupling among the states. On the other hand, the BO treatment provides two important quantities, namely, the adiabatic potential energy surfaces (PESs) and the nonadiabatic coupling terms (NACTs) determining the forces, which control the motion of the nuclei in a molecule. The NACTs play a major role in photoexcitation spectra, charge transfer chemical reactions, ferroelectric property and other processes, where significant anomalies are observed between single and multiple PES(s) results. Since the NACTs often exhibit singularity at the close vicinity of degenerate states forming conical intersections (CIs), such coupling terms could break the symmetry of the molecular processes changing the observables qualitatively.

Chemical Physics (physics.chem-ph); Quantum Physics (quant-ph)

arXiv:2610.41898 [physics.chem-ph]

(or arXiv:2610.41898v1 [physics.chem-ph] for this version)

https://doi.org/10.48550/arXiv.2610.41898 Focus to learn more arXiv-issued DOI via DataCite (pending registration)

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