A theoretical study of vibronic coupling in the photoelectron spectra of Al<sub>6</sub>N<sup>−</sup>

Pandey, Rishabh Kumar; Srikanth, Korutla; Tak, Anuj; Kumar, Abhishek; Tammineni, Rajagopala Rao

doi:10.1039/d3cp00836c

Cited by 2 publications

(1 citation statement)

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“…Therefore, in this study, the photodetachment spectra of CAl 3 Si – are theoretically resolved, and the nonadiabatic effects among nearly spaced X̃, Ã, B̃ and D̃, Ẽ bands are unfolded. To address this objective, various methodologies have been proposed in the literature, employing diabatic coupling schemes, including the beyond Born–Oppenheimer (BBO) approach, , direct dynamics (DD) approach, − exact factorization (EF) scheme, − and vibronic coupling theory (VCT). − In our study, we opted for the computationally viable VCT − developed by Köppel et al, which has demonstrated success in various photodetachment processes. − Under the framework of this methodology, the optimized geometry is obtained first, and later ab initio single-point energy calculations are performed for the first six electronic states of CAl 3 Si (outlined in the Computational and Theoretical Approach Section). Later, these calculated energies were utilized for the determination of the Hamiltonian parameters.…”

Section: Introductionmentioning

confidence: 99%

Resolving the Experimental Photoelectron Spectra of CAl₃Si^–

Pandey,

Srikanth,

Tripathi

et al. 2024

J. Phys. Chem. A

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The experimental photoelectron spectra concerning the six electronic states of CAl 3 Si − are resolved through electronic structure calculations and quantum nuclear dynamics in this study. It incorporates a model diabatic Hamiltonian to evaluate the coupling parameters and fit the potential energy curves (PECs). The analysis of these PECs showed us that there are sufficient nonadiabatic effects in the photoelectron spectra through the presence of various conical intersections. Poisson intensity distributions (PIDs) and the wave packet density plots are utilized for assigning the fundamental and first overtone excitations. The nuclear dynamics study is accomplished by employing timedependent (TD) and time-independent (TI) quantum chemistry methods. Ultimately, our theoretical results concurred well with the experimental findings exhibiting vibronic coupling amidst the nearly positioned electronic states.

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