Research Papers in Physics and Astronomy

 

Date of this Version

2013

Citation

Published in SAR and QSAR in Environmental Research, 2013 Vol. 24, No. 8, 647–659,

http://dx.doi.org/10.1080/1062936X.2013.792873

Comments

Copyright © 2013 Taylor & Francis. Used by permission.

Abstract

Calculated energies of lowest unoccupied molecular orbitals (LUMOs) are frequently employed as descriptors in studies of quantitative structure–activity relationships and linear free energy relationships involving electron transfer. However, the quantum chemical programs with which these are carried out, whether Hartree–Fock or density functional theory, do not treat orbitals of different character, for example, C=C π* and C-Cl σ*, consistently, nor is there consistency among different families of compounds. These problems can be ameliorated with the use of the experimental equivalent of the LUMO energy, the vertical attachment energy (VAE), or by shifting and scaling LUMO energies to a training set of available VAEs in similar compounds. Examples from the literature are used to illustrate these points.

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