| Autor: |
Kanakati AK; School of Chemistry, University of Hyderabad, Hyderabad 500 046, India., Mahapatra S; School of Chemistry, University of Hyderabad, Hyderabad 500 046, India. |
| Jazyk: |
angličtina |
| Zdroj: |
The Journal of chemical physics [J Chem Phys] 2021 Feb 07; Vol. 154 (5), pp. 054313. |
| DOI: |
10.1063/5.0039923 |
| Abstrakt: |
Nuclear dynamics in the first six vibronically coupled electronic states of pentafluorobenzene radical cation is studied with the aid of the standard vibronic coupling theory and quantum dynamical methods. A model 6 × 6 vibronic Hamiltonian is constructed in a diabatic electronic basis using symmetry selection rules and a Taylor expansion of the elements of the electronic Hamiltonian in terms of the normal coordinate of vibrational modes. Extensive ab initio quantum chemistry calculations are carried out for the adiabatic electronic energies to establish the diabatic potential energy surfaces and their coupling surfaces. Both time-independent and time-dependent quantum mechanical methods are employed to perform nuclear dynamics calculations. The vibronic spectrum of the electronic states is calculated, assigned, and compared with the available experimental results. Internal conversion dynamics of electronic states is examined to assess the impact of various couplings on the nuclear dynamics. The impact of increasing fluorination of the parent benzene radical cation on its radiative emission is examined and discussed. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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