Analysis of Bonding Patterns in the Valence Isoelectronic Series O-3, S-3, SO2, and OS2 in Terms of Oriented Quasi-Atomic Molecular Orbitals

TitleAnalysis of Bonding Patterns in the Valence Isoelectronic Series O-3, S-3, SO2, and OS2 in Terms of Oriented Quasi-Atomic Molecular Orbitals
Publication TypeJournal Article
Year of Publication2010
AuthorsGlezakou VA, Elbert ST, Xantheas SS, Ruedenberg K
Journal TitleJournal of Physical Chemistry A
Volume114
Pages8923-8931
Date Published8/26
ISBN Number1089-5639
Accession NumberISI:000280962400049
Keywordschappuis-band absorption, electronic wave-functions, excited-states, gaussian-basis sets, intersection seam, intrinsic local constituents, ozone molecule, POTENTIAL-ENERGY SURFACES, stratospheric ozone, vibrational frequencies
Abstract

A novel analysis of the chemical bonding pattern in the valence isoelectronic series of triatomic molecules O-3, S-3, SO2, and OS2 is reported It is based on examining the bond order matrix elements between the oriented localized molecular orbitals (OLMOs) that are localized on the three individual atoms. left (L), center (C), and right (R) The analysis indicates that there is a (L-C) and (C-R) pi-bonding interaction and a (L-R) pi-antibonding interaction. It supports the earlier proposed "partial biradical" interpretation of these systems, which had recently been challenged The degree of biradical character is shown to increase from SO2 to S-3 to O-3 to OS2.

URL<Go to ISI>://000280962400049
DOI10.1021/Jp105025d