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Correlation Analysis of Chemical Bonds (CACB) II: Quantum Mechanical Operators for Classical Chemical Concepts

Yamasaki, Terumasa and Mainz, Daniel T. and Goddard, William A., III (2000) Correlation Analysis of Chemical Bonds (CACB) II: Quantum Mechanical Operators for Classical Chemical Concepts. Journal of Physical Chemistry A, 104 (11). pp. 2221-2229. ISSN 1089-5639. http://resolver.caltech.edu/CaltechAUTHORS:20170519-142630122

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Abstract

We apply correlation analysis of chemical bonds (CACB) to simple organic reaction paths. CACB, an operator-based formalism for analyzing the electronic structure for molecule, clarifies how bond exchange processes relate to changes in covalent bond orders and bond interaction coefficients. For single bond-exchange processes, the bonds correlation typically is negative for interchanging bonds. For two bond-exchange processes, this coefficient can be either negative or slightly positive near zero, reflecting the nature of the bond exchange process. The simplest formalism can, sometimes, lead to unphysical values for the atomic valence and the bonds correlation coefficients. We analyzed the origin of this behavior and attributed it to the non-Hermitian property of the operator. We show how to avoid this problem by symmetrizing the operator through use of orthogonal atomic orbitals.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp9942320DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp9942320PublisherArticle
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2000 American Chemical Society. Received: December 1, 1999. Publication Date (Web): February 19, 2000. The MSC thanks Asahi Chemical and NSF (CHE 95-100368) for research funding. The MSC facilities used in this research are supported by grants from NSF-MRI, DOE-ASCI, DOE-MURI, BP Amoco, Chevron Corp., Beckman Institute, Exxon, Seiko-Epson, Owens-Corning, Avery-Dennison, Dow Chemical, and 3M.
Funders:
Funding AgencyGrant Number
Asahi ChemicalUNSPECIFIED
NSFCHE 95-100368
Department of Energy (DOE)UNSPECIFIED
BP AmocoUNSPECIFIED
Chevron CorporationUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
ExxonUNSPECIFIED
Seiko-EpsonUNSPECIFIED
Owens-CorningUNSPECIFIED
Avery-DennisonUNSPECIFIED
Dow Chemical CompanyUNSPECIFIED
3MUNSPECIFIED
Record Number:CaltechAUTHORS:20170519-142630122
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20170519-142630122
Official Citation:Correlation Analysis of Chemical Bonds (CACB) II:  Quantum Mechanical Operators for Classical Chemical Concepts Terumasa Yamasaki, Daniel T. Mainz, and William A. Goddard, III The Journal of Physical Chemistry A 2000 104 (11), 2221-2229 DOI: 10.1021/jp9942320
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77606
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:19 May 2017 21:32
Last Modified:19 May 2017 21:32

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