Literature DB >> 20586467

How ambiguous is the local kinetic energy?

James S M Anderson1, Paul W Ayers, Juan I Rodriguez Hernandez.   

Abstract

The local kinetic energy and the closely related local electronic stress tensor are commonly used to elucidate chemical bonding patterns, especially for covalent bonds. We use three different approaches-transformation properties of the stress tensor, quasiprobability distributions, and the virial theorem from density-functional theory-to clarify the inherent ambiguity in these quantities, discussing the implications for analyses based on the local kinetic energy and stress tensor. An expansive-but not universal-family of local kinetic energy forms that includes the most common choices and is suitable for both chemical-bonding and atoms-in-molecule analysis is derived. A family of local electronic stress tensors is also derived. Several local kinetic energy functions that are mathematically justified, but unlikely to be conceptually useful, are derived. The implications of these forms for atoms-in-molecule analysis are discussed.

Year:  2010        PMID: 20586467     DOI: 10.1021/jp1029745

Source DB:  PubMed          Journal:  J Phys Chem A        ISSN: 1089-5639            Impact factor:   2.781


  5 in total

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5.  Simultaneous Visualization of Covalent and Noncovalent Interactions Using Regions of Density Overlap.

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Journal:  J Chem Theory Comput       Date:  2014-06-30       Impact factor: 6.006

  5 in total

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