Intrinsic Resolution of Molecular Electronic Wave Functions and Energies in Terms of Quasi-atoms and Their Interactions

dc.contributor.author Gordon, Mark
dc.contributor.author Schmidt, Michael W.
dc.contributor.author Gordon, Mark
dc.contributor.author Ruedenberg, Klaus
dc.contributor.department Chemistry
dc.contributor.department Ames Laboratory
dc.date.accessioned 2022-03-01T22:44:26Z
dc.date.available 2022-03-01T22:44:26Z
dc.date.issued 2017-02-09
dc.description.abstract A general intrinsic energy resolution has been formulated for strongly correlated wave functions in the full molecular valence space and its subspaces. The information regarding the quasi-atomic organization of the molecular electronic structure is extracted from the molecular wave function without introducing any additional postulated model state wave functions. To this end, the molecular wave function is expressed in terms of quasi-atomic molecular orbitals, which maximize the overlap between subspaces of the molecular orbital space and the free-atom orbital spaces. As a result, the molecular wave function becomes the superposition of a wave function representing the juxtaposed nonbonded quasi-atoms and a wave function describing the interatomic electron migrations that create bonds through electron sharing. The juxtaposed nonbonded quasi-atoms are shown to consist of entangled quasi-atomic states from different atoms. The binding energy is resolved as a sum of contributions that are due to quasi-atom formation, quasiclassical electrostatic interactions, and interatomic interferences caused by electron sharing. The contributions are further resolved according to orbital interactions. The various transformations that generate the analysis are determined by criteria that are independent of the working orbital basis used for calculating the molecular wave function. The theoretical formulation of the resolution is quantitatively validated by an application to the C2 molecule.
dc.description.comments This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry A, copyright © 2017 American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/acs.jpca.6b10911, Posted with permission.
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/JvNVknev
dc.language.iso en_US
dc.publisher American Chemical Society
dc.source.uri https://doi.org/10.1021/acs.jpca.6b10911 *
dc.title Intrinsic Resolution of Molecular Electronic Wave Functions and Energies in Terms of Quasi-atoms and Their Interactions
dc.type Article
dspace.entity.type Publication
relation.isAuthorOfPublication 1a5927c0-5a5f-440e-86e0-9da8dc6afda0
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
relation.isOrgUnitOfPublication 25913818-6714-4be5-89a6-f70c8facdf7e
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