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Reimers, Jeffrey R.; Hush, Noel S., E-mail: jeffrey.reimers@uts.edu.au, E-mail: noel.hush@sydney.edu.au2017
AbstractAbstract
[en] Highlights: • Transition-state spectra are calculated over a wide parameter region. • Spectral and temporal responses may be simple or quite complex. • Surface hopping methods fail to describe spectra usually classified as “non-adiabatic”. • Transition-state spectroscopy embodies quantum entanglement. 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.
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S0009261417303998; Available from http://dx.doi.org/10.1016/j.cplett.2017.04.070; Copyright (c) 2017 Elsevier B.V. All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
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