View in EDS

Revealing Electron-Electron Interactions within Lewis Pairs in Chemical Systems.

Saved in:
Bibliographic Details
Title: Revealing Electron-Electron Interactions within Lewis Pairs in Chemical Systems.
Authors: Proud, Adam Jonathan, Sheppard, Brendan James Henry, Pearson, Jason Kenneth jpearson@upei.ca
Source: Journal of the American Chemical Society. 1/10/2018, Vol. 140 Issue 1, p219-228. 10p.
Subjects: Electron-electron interactions, Lewis pairs (Chemistry), Chemical structure, Valence shell electron pair repulsion, Molecular structure
Abstract: The so-called "Lewis pair" is a ubiquitous phenomenon in chemistry and is often used as an intuitive construct to predict and rationalize chemical structure and behavior. Concepts from the very general Valence Shell Electron Pair Repulsion (VSEPR) model to the most esoteric reaction mechanism routinely rely on the notion that electrons tend to exist in pairs and that these pairs can be thought of as being localized to a particular region of space. It is precisely this localization that allows one to intuit how these pairs might behave, generally speaking, so that reasonable predictions may be made regarding molecular structure, intermolecular interactions, property trends, and reaction mechanisms, etc. Of course, it is rather unfortunate that the Lewis model is entirely qualitative and yields no information regarding how any specific electron pair is distributed. Here we demonstrate a novel electronic structure analysis technique that predicts and analyzes precise quantitative details about the relative and absolute distribution of individual electron pairs. This Single Electron Pair Distribution Analysis (SEPDA) reveals quantitative details about the distribution of the well-known Lewis pairs, such as how they are distributed in space and how their relative velocities change in various chemical contexts. We show that these distributions allow one to image the explicitly pairwise electronic behavior of bonds and lone pairs. We further demonstrate how this electronic behavior changes with several conditions to explore the nature of the covalent chemical bond, non-covalent interactions, bond formation, and exotic 3-center- 2-electron species. It is shown that indications of the strength of bonded and non-bonded interactions may also be gleaned from such distributions and SEPDA can be used as a tool to differentiate between interaction types. We anticipate that SEPDA will be of broad utility in a wide variety of chemical contexts because it affords a very detailed, visual and intuitive analysis technique that is generally applicable. [ABSTRACT FROM AUTHOR]
Copyright of Journal of the American Chemical Society 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
Header DbId: egs
DbLabel: Engineering Source
An: 127320110
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
IllustrationInfo
Items – Name: Title
  Label: Title
  Group: Ti
  Data: Revealing Electron-Electron Interactions within Lewis Pairs in Chemical Systems.
– Name: Author
  Label: Authors
  Group: Au
  Data: <searchLink fieldCode="AR" term="%22Proud%2C+Adam+Jonathan%22">Proud, Adam Jonathan</searchLink><br /><searchLink fieldCode="AR" term="%22Sheppard%2C+Brendan+James+Henry%22">Sheppard, Brendan James Henry</searchLink><br /><searchLink fieldCode="AR" term="%22Pearson%2C+Jason+Kenneth%22">Pearson, Jason Kenneth</searchLink><i> jpearson@upei.ca</i>
– Name: TitleSource
  Label: Source
  Group: Src
  Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Chemical+Society%22">Journal of the American Chemical Society</searchLink>. 1/10/2018, Vol. 140 Issue 1, p219-228. 10p.
– Name: Subject
  Label: Subjects
  Group: Su
  Data: <searchLink fieldCode="DE" term="%22Electron-electron+interactions%22">Electron-electron interactions</searchLink><br /><searchLink fieldCode="DE" term="%22Lewis+pairs+%28Chemistry%29%22">Lewis pairs (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+structure%22">Chemical structure</searchLink><br /><searchLink fieldCode="DE" term="%22Valence+shell+electron+pair+repulsion%22">Valence shell electron pair repulsion</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+structure%22">Molecular structure</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: The so-called "Lewis pair" is a ubiquitous phenomenon in chemistry and is often used as an intuitive construct to predict and rationalize chemical structure and behavior. Concepts from the very general Valence Shell Electron Pair Repulsion (VSEPR) model to the most esoteric reaction mechanism routinely rely on the notion that electrons tend to exist in pairs and that these pairs can be thought of as being localized to a particular region of space. It is precisely this localization that allows one to intuit how these pairs might behave, generally speaking, so that reasonable predictions may be made regarding molecular structure, intermolecular interactions, property trends, and reaction mechanisms, etc. Of course, it is rather unfortunate that the Lewis model is entirely qualitative and yields no information regarding how any specific electron pair is distributed. Here we demonstrate a novel electronic structure analysis technique that predicts and analyzes precise quantitative details about the relative and absolute distribution of individual electron pairs. This Single Electron Pair Distribution Analysis (SEPDA) reveals quantitative details about the distribution of the well-known Lewis pairs, such as how they are distributed in space and how their relative velocities change in various chemical contexts. We show that these distributions allow one to image the explicitly pairwise electronic behavior of bonds and lone pairs. We further demonstrate how this electronic behavior changes with several conditions to explore the nature of the covalent chemical bond, non-covalent interactions, bond formation, and exotic 3-center- 2-electron species. It is shown that indications of the strength of bonded and non-bonded interactions may also be gleaned from such distributions and SEPDA can be used as a tool to differentiate between interaction types. We anticipate that SEPDA will be of broad utility in a wide variety of chemical contexts because it affords a very detailed, visual and intuitive analysis technique that is generally applicable. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of the American Chemical Society 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.)
PLink https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=127320110
RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1021/jacs.7b08935
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 10
        StartPage: 219
    Subjects:
      – SubjectFull: Electron-electron interactions
        Type: general
      – SubjectFull: Lewis pairs (Chemistry)
        Type: general
      – SubjectFull: Chemical structure
        Type: general
      – SubjectFull: Valence shell electron pair repulsion
        Type: general
      – SubjectFull: Molecular structure
        Type: general
    Titles:
      – TitleFull: Revealing Electron-Electron Interactions within Lewis Pairs in Chemical Systems.
        Type: main
  BibRelationships:
    HasContributorRelationships:
      – PersonEntity:
          Name:
            NameFull: Proud, Adam Jonathan
      – PersonEntity:
          Name:
            NameFull: Sheppard, Brendan James Henry
      – PersonEntity:
          Name:
            NameFull: Pearson, Jason Kenneth
    IsPartOfRelationships:
      – BibEntity:
          Dates:
            – D: 10
              M: 01
              Text: 1/10/2018
              Type: published
              Y: 2018
          Identifiers:
            – Type: issn-print
              Value: 00027863
          Numbering:
            – Type: volume
              Value: 140
            – Type: issue
              Value: 1
          Titles:
            – TitleFull: Journal of the American Chemical Society
              Type: main
ResultId 1