A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity

Reimers, Jeffrey R., McKemmish, Laura K., McKenzie, Ross H. and Hush, Noel S. (2015) A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity. Physical Chemistry Chemical Physics, 17 38: 24598-24617. doi:10.1039/c5cp02236c


Author Reimers, Jeffrey R.
McKemmish, Laura K.
McKenzie, Ross H.
Hush, Noel S.
Title A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity
Journal name Physical Chemistry Chemical Physics   Check publisher's open access policy
ISSN 1463-9076
1463-9084
Publication date 2015-10-14
Year available 2015
Sub-type Article (original research)
DOI 10.1039/c5cp02236c
Open Access Status Not Open Access
Volume 17
Issue 38
Start page 24598
End page 24617
Total pages 20
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Language eng
Formatted abstract
While diabatic approaches are ubiquitous for the understanding of electron-transfer reactions and have been mooted as being of general relevance, alternate applications have not been able to unify the same wide range of observed spectroscopic and kinetic properties. The cause of this is identified as the fundamentally different orbital configurations involved: charge-transfer phenomena involve typically either 1 or 3 electrons in two orbitals whereas most reactions are typically closed shell. As a result, two vibrationally coupled electronic states depict charge-transfer scenarios whereas three coupled states arise for closed-shell reactions of non-degenerate molecules and seven states for the reactions implicated in the aromaticity of benzene. Previous diabatic treatments of closed-shell processes have considered only two arbitrarily chosen states as being critical, mapping these states to those for electron transfer. We show that such effective two-state diabatic models are feasible but involve renormalized electronic coupling and vibrational coupling parameters, with this renormalization being property dependent. With this caveat, diabatic models are shown to provide excellent descriptions of the spectroscopy and kinetics of the ammonia inversion reaction, proton transfer in N2H7+, and aromaticity in benzene. This allows for the development of a single simple theory that can semi-quantitatively describe all of these chemical phenomena, as well as of course electron-transfer reactions. It forms a basis for understanding many technologically relevant aspects of chemical reactions, condensed-matter physics, chemical quantum entanglement, nanotechnology, and natural or artificial solar energy capture and conversion.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Mathematics and Physics
Official 2016 Collection
 
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