Chemical Physics Letters, Vol.683, 467-477, 2017
Relating transition-state spectroscopy to standard chemical spectroscopic processes
Transition-state spectra are mapped out using generalized adiabatic electron-transfer theory. This simple model depicts diverse chemical properties, from aromaticity, through bound reactions such as isomerizations and atom-transfer processes with classic transition states, to processes often described as being "non-adiabatic", to those in the "inverted" region that become slower as they are made more exothermic. Predictably, the Born-Oppenheimer approximation is found inadequate for modelling transition-state spectra in the weak-coupling limit. In this limit, the adiabatic Born-Huang approximation is found to perform much better than non-adiabatic surface-hopping approaches. Transition-state spectroscopy is shown to involve significant quantum entanglement between electronic and nuclear motion. (C) 2017 Elsevier B.V. All rights reserved.
Keywords:Adiabatic electron-transfer theory;Quantum dynamics;Born-Oppenheimer breakdown;Chemical entanglement;Transition-state theory;Non-adiabatic reactions;Born-Huang approximation