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Published on: July 27, 2018
Vibronic coupling effects in the photoelectron spectra of LiB6
Rishabh Kumar Pandey1, Bingyu Cui1
1School of Science and Engineering, The Chinese University of Hong Kong (Shenzhen), Longgang, Shenzhen, Guangdong 518172, P. R. China. rishabhp109@gmail.com.
Abstract:
This present article exhibits a theoretical exploration of vibronic coupling effects in the 193 nm experimental photoelectron spectra of LiB6-, focusing on its six lowest-lying electronic states. Based on the adiabatic potential energy curves derived from ab initio calculations, we construct a diabatic vibronic Hamiltonian and perform nuclear dynamics calculations by adopting TD and TI formulations of quantum mechanics, considering adiabatic (uncoupled) and non-adiabatic (coupled) scenarios. In this study, Poisson statistics provided vibronic intensity progressions from an adiabatic perspective, and the rapid transfer of electronic population confirmed the magnitude of the non-adiabatic coupling. Our final simulated spectrum reproduces the peaks of the experimental spectrum with good agreement, enabling detailed vibronic interpretation of the photoelectron spectrum of LiB6-.
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