Open AccessPseudo Jahn−Teller Origin of the Proton Tunneling in Zundel Cation Containing Water Clusters
Author(s) -
Ion Geru,
Natalia Gorinchoy,
Iolanta Bălan
Publication year - 2021
Publication title -
ukrainian journal of physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.213
H-Index - 17
eISSN - 2071-0194
pISSN - 2071-0186
DOI - 10.15407/ujpe57.11.1149
Subject(s) - jahn–teller effect , ab initio , excited state , adiabatic process , proton , potential energy , quantum tunnelling , vibronic coupling , chemistry , ab initio quantum chemistry methods , potential energy surface , atomic physics , water dimer , cluster (spacecraft) , molecular physics , molecule , physics , ion , condensed matter physics , hydrogen bond , quantum mechanics , organic chemistry , computer science , programming language
The pseudo Jahn–Teller (PJT) origin of the proton transfer barrier in the Zundel cation at different O–O distances and in an H5O2+(H2O)4 cluster is revealed by means of ab initio calculations of their electronic structures and the adiabatic potential energy curves. The vibronic constants in this approach were estimated by fitting the ab initio calculated adiabatic potential to its analytical expression. It is shown also that the high-symmetry nuclear configurations ofproton-centered water clusters of the type H+(H2O)n (n = 6, 4, 3) are unstable with respect to the low-symmetry nuclear distortions leading to forming the dihydronium cation H5O2+ and the appropriate number of water molecules: H2n + 1On+ → (n – 2)H2O + H5O2+. The reason for this instability and the subsequent decay is the PJT coupling between the ground and excited electronic states.