Identification and Characterization of Molecular Bonding Structures by ab initio Quasi-Atomic Orbital Analyses

Published on 2017-11-14T18:51:17Z (GMT) by
The quasi-atomic analysis of <i>ab initio</i> electronic wave functions in full valence spaces, which was developed in preceding papers, yields oriented quasi-atomic orbitals in terms of which the <i>ab initio</i> molecular wave function and energy can be expressed. These oriented quasi-atomic orbitals are the rigorous <i>ab initio</i> counterparts to the conceptual bond forming atomic hybrid orbitals of qualitative chemical reasoning. In the present work, the quasi-atomic orbitals are identified as bonding orbitals, lone pair orbitals, radical orbitals, vacant orbitals and orbitals with intermediate character. A program determines the bonding characteristics of all quasi-atomic orbitals in a molecule on the basis of their occupations, bond orders, kinetic bond orders, hybridizations and local symmetries. These data are collected in a record and provide the information for a comprehensive understanding of the synergism that generates the bonding structure that holds the molecule together. Applications to a series of molecules exhibit the complete bonding structures that are embedded in their <i>ab initio</i> wave functions. For the strong bonds in a molecule, the quasi-atomic orbitals provide quantitative <i>ab initio</i> amplifications of the Lewis dot symbols. Beyond characterizing strong bonds, the quasi-atomic analysis also yields an understanding of the weak interactions, such as vicinal, hyperconjugative and radical stabilizations, which can make substantial contributions to the molecular bonding structure.

Cite this collection

West, Aaron C.; Duchimaza-Heredia, Juan J.; Gordon, Mark S.; Ruedenberg, Klaus (2017): Identification and Characterization of Molecular Bonding Structures

by ab initio Quasi-Atomic Orbital Analyses. ACS Publications.

https://doi.org/10.1021/acs.jpca.7b07054

Retrieved: 22:22, Nov 24, 2017 (GMT)