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

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 non-bonded juxtaposed 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. Lastly, the theoretical formulation of the resolution is quantitatively validatedmore » by an application to the C 2 molecule.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1355451
Report Number(s):
IS-J-9300
Journal ID: ISSN 1089-5639
Grant/Contract Number:  
CHE-1147446; CHE-1565888; AC02-07CH11358
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 121; Journal Issue: 5; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

West, Aaron C., Schmidt, Michael W., Gordon, Mark S., and Ruedenberg, Klaus. Intrinsic Resolution of Molecular Electronic Wave Functions and Energies in Terms of Quasi-atoms and Their Interactions. United States: N. p., 2017. Web. doi:10.1021/acs.jpca.6b10911.
West, Aaron C., Schmidt, Michael W., Gordon, Mark S., & Ruedenberg, Klaus. Intrinsic Resolution of Molecular Electronic Wave Functions and Energies in Terms of Quasi-atoms and Their Interactions. United States. doi:10.1021/acs.jpca.6b10911.
West, Aaron C., Schmidt, Michael W., Gordon, Mark S., and Ruedenberg, Klaus. Mon . "Intrinsic Resolution of Molecular Electronic Wave Functions and Energies in Terms of Quasi-atoms and Their Interactions". United States. doi:10.1021/acs.jpca.6b10911. https://www.osti.gov/servlets/purl/1355451.
@article{osti_1355451,
title = {Intrinsic Resolution of Molecular Electronic Wave Functions and Energies in Terms of Quasi-atoms and Their Interactions},
author = {West, Aaron C. and Schmidt, Michael W. and Gordon, Mark S. and Ruedenberg, Klaus},
abstractNote = {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 non-bonded juxtaposed 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. Lastly, the theoretical formulation of the resolution is quantitatively validated by an application to the C2 molecule.},
doi = {10.1021/acs.jpca.6b10911},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 5,
volume = 121,
place = {United States},
year = {Mon Jan 30 00:00:00 EST 2017},
month = {Mon Jan 30 00:00:00 EST 2017}
}

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