Canonical Force Distributions in Pairwise Interatomic Interactions from the Perspective of the Hellmann-Feynman Theorem.
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| Title: | Canonical Force Distributions in Pairwise Interatomic Interactions from the Perspective of the Hellmann-Feynman Theorem. |
|---|---|
| Authors: | Walton, Jay R.1, Rivera-Rivera, Luis A.2 rivera@chem.tamu.edu, Lucchese, Robert R.2, Bevan, John W.2 |
| Source: | Journal of Physical Chemistry A. 5/26/2016, Vol. 120 Issue 20, p3718-3725. 8p. |
| Subjects: | Interatomic angles, Hellmann-Feynman theorem, Van der Waals forces, Canonical transformations, Coulomb functions |
| Abstract: | Force-based canonical approaches have recently given a unified but different viewpoint on the nature of bonding in pairwise interatomic interactions. Differing molecular categories (covalent, ionic, van der Waals, hydrogen, and halogen bonding) of representative interatomic interactions with binding energies ranging from 1.01 to 1072.03 kJ/mol have been modeled canonically giving a rigorous semiempirical verification to high accuracy. However, the fundamental physical basis expected to provide the inherent characteristics of these canonical transformations has not yet been elucidated. Subsequently, it was shown through direct numerical differentiation of these potentials that their associated force curves have canonical shapes. However, this approach to analyzing force results in inherent loss of accuracy coming from numerical differentiation of the potentials. We now show that this serious obstruction can be avoided by directly demonstrating the canonical nature of force distributions from the perspective of the Hellmann-Feynman theorem. This requires only differentiation of explicitly known Coulombic potentials, and we discuss how this approach to canonical forces can be used to further explain the nature of chemical bonding in pairwise interatomic interactions. All parameter values used in the canonical transformation are determined through explicit physical based algorithms, and it does not require direct consideration of electron correlation effects. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 115974834 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Canonical Force Distributions in Pairwise Interatomic Interactions from the Perspective of the Hellmann-Feynman Theorem. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Walton%2C+Jay+R%2E%22">Walton, Jay R.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Rivera-Rivera%2C+Luis+A%2E%22">Rivera-Rivera, Luis A.</searchLink><relatesTo>2</relatesTo><i> rivera@chem.tamu.edu</i><br /><searchLink fieldCode="AR" term="%22Lucchese%2C+Robert+R%2E%22">Lucchese, Robert R.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Bevan%2C+John+W%2E%22">Bevan, John W.</searchLink><relatesTo>2</relatesTo> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+A%22">Journal of Physical Chemistry A</searchLink>. 5/26/2016, Vol. 120 Issue 20, p3718-3725. 8p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Interatomic+angles%22">Interatomic angles</searchLink><br /><searchLink fieldCode="DE" term="%22Hellmann-Feynman+theorem%22">Hellmann-Feynman theorem</searchLink><br /><searchLink fieldCode="DE" term="%22Van+der+Waals+forces%22">Van der Waals forces</searchLink><br /><searchLink fieldCode="DE" term="%22Canonical+transformations%22">Canonical transformations</searchLink><br /><searchLink fieldCode="DE" term="%22Coulomb+functions%22">Coulomb functions</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Force-based canonical approaches have recently given a unified but different viewpoint on the nature of bonding in pairwise interatomic interactions. Differing molecular categories (covalent, ionic, van der Waals, hydrogen, and halogen bonding) of representative interatomic interactions with binding energies ranging from 1.01 to 1072.03 kJ/mol have been modeled canonically giving a rigorous semiempirical verification to high accuracy. However, the fundamental physical basis expected to provide the inherent characteristics of these canonical transformations has not yet been elucidated. Subsequently, it was shown through direct numerical differentiation of these potentials that their associated force curves have canonical shapes. However, this approach to analyzing force results in inherent loss of accuracy coming from numerical differentiation of the potentials. We now show that this serious obstruction can be avoided by directly demonstrating the canonical nature of force distributions from the perspective of the Hellmann-Feynman theorem. This requires only differentiation of explicitly known Coulombic potentials, and we discuss how this approach to canonical forces can be used to further explain the nature of chemical bonding in pairwise interatomic interactions. All parameter values used in the canonical transformation are determined through explicit physical based algorithms, and it does not require direct consideration of electron correlation effects. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/acs.jpca.6b03343 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 8 StartPage: 3718 Subjects: – SubjectFull: Interatomic angles Type: general – SubjectFull: Hellmann-Feynman theorem Type: general – SubjectFull: Van der Waals forces Type: general – SubjectFull: Canonical transformations Type: general – SubjectFull: Coulomb functions Type: general Titles: – TitleFull: Canonical Force Distributions in Pairwise Interatomic Interactions from the Perspective of the Hellmann-Feynman Theorem. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Walton, Jay R. – PersonEntity: Name: NameFull: Rivera-Rivera, Luis A. – PersonEntity: Name: NameFull: Lucchese, Robert R. – PersonEntity: Name: NameFull: Bevan, John W. IsPartOfRelationships: – BibEntity: Dates: – D: 26 M: 05 Text: 5/26/2016 Type: published Y: 2016 Identifiers: – Type: issn-print Value: 10895639 Numbering: – Type: volume Value: 120 – Type: issue Value: 20 Titles: – TitleFull: Journal of Physical Chemistry A Type: main |
| ResultId | 1 |
