Open AccessPseudo Jahn-Teller Origin of the Proton-transfer Energy Barrier in the Hydrogen-bonded [FHF]-System
Author(s) -
Natalia Gorinchoy,
Iolanta Bălan,
V. Z. Polinger,
И. Б. Берсукер
Publication year - 2021
Publication title -
chemistry journal of moldova
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.275
H-Index - 5
eISSN - 2345-1688
pISSN - 1857-1727
DOI - 10.19261/cjm.2021.834
Subject(s) - chemistry , jahn–teller effect , excited state , proton , adiabatic process , atomic physics , ground state , zero point energy , ab initio , symmetry (geometry) , potential energy , hydrogen , fluorine , molecular physics , ion , physics , quantum mechanics , geometry , mathematics , organic chemistry
The results of ab initio calculations of the adiabatic potential energy surfaces for the proton-bound [FHF]- system at different F-F distances have been rationalized in the framework of the vibronic theory. It is shown that the instability of the symmetric D∞h structure at increased F∙∙∙F distances and the proton displacement to one of the fluorine atoms is due to the pseudo Jahn–Teller mixing of the ground 1Σg electronic state with the lowest excited state of 1Σu symmetry through the asymmetric σu vibrational mode.