title: Predicting bond strength from a single Hartree-Fock ground state using the localized pair model.
abstract: We present an application of the recently introduced Localized Pair Model (LPM) [Z. A. Zielinksi and J. K. Pearson, Comput. Theor. Chem., 2013, 1003, 7990] to characterize and quantify properties of the chemical bond in a series of substituted benzoic acid molecules. By computing interelectronic distribution functions for doubly-occupied Edmiston-Ruedenberg localized molecular orbitals (LMOs), we show that chemically intuitive electron pairs may be uniquely classified and bond strength may be predicted with remarkable accuracy. Specifically, the HF/u6-311G(d,p) level (where u denotes a complete uncontraction of the basis set) is used to generate the relevant LMOs and their respective interelectronic distribution functions can be linearly correlated to the well-known Hammett σp or σm parameters with near-unity correlation coefficients.
authors.affiliation: Department of Chemistry, University of Prince Edward Island, 550 University Avenue, Charlottetown, PE, Canada. jpearson@upei.ca.
authors.forename: Dylan C
authors.initials: DC
authors.lastname: Hennessey
authors.forename: Brendan J H
authors.initials: BJ
authors.lastname: Sheppard
authors.forename: Dalton E C K
authors.initials: DE
authors.lastname: Mackenzie
authors.forename: Jason K
authors.initials: JK
authors.lastname: Pearson