Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Testing the nature of reaction coordinate describing interaction of H-2 with carbonyl carbon, activated by Lewis acid complexation, and the Lewis basic solvent: A Born-Oppenheimer molecular dynamics study with explicit solvent
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0003-1028-3035
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Number of Authors: 22017 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 147, no 9, article id 094302Article in journal (Refereed) Published
Abstract [en]

Using Born-Oppenheimer molecular dynamics (BOMD), we explore the nature of interactions between H-2 and the activated carbonyl carbon, C(carbonyl), of the acetone-B(C6F5)(3) adduct surrounded by an explicit solvent (1,4-dioxane). BOMD simulations at finite (non-zero) temperature with an explicit solvent produced long-lasting instances of significant vibrational perturbation of the H-H bond and H2-polarization at C(carbonyl). As far as the characteristics of H2 are concerned, the dynamical transient state approximates the transition-state of the heterolytic H2-cleavage. The culprit is the concerted interactions of H2 with C( carbonyl) and a number of Lewis basic solvent molecules- i. e., the concerted C(carbonyl) ...H2... solvent interactions. On one hand, the results presented herein complement the mechanistic insight gained from our recent transition-state calculations, reported separately from this article. But on the other hand, we now indicate that an idea of the sufficiency of just one simple reaction coordinate in solution-phase reactions can be too simplistic and misleading. This article goes in the footsteps of the rapidly strengthening approach of investigating molecular interactions in large molecular systems via computational experimentation employing, primarily, ab initio molecular dynamics describing reactants-interaction without constraints of the preordained reaction coordinate and/or foreknowledge of the sampling order parameters.

Place, publisher, year, edition, pages
2017. Vol. 147, no 9, article id 094302
National Category
Chemical Sciences Physical Sciences
Identifiers
URN: urn:nbn:se:su:diva-180165DOI: 10.1063/1.4999708ISI: 000409946200016PubMedID: 28886629OAI: oai:DiVA.org:su-180165DiVA, id: diva2:1415704
Available from: 2020-03-19 Created: 2020-03-19 Last updated: 2020-03-19Bibliographically approved

Open Access in DiVA

No full text in DiVA

Other links

Publisher's full textPubMed

Search in DiVA

By author/editor
Heshmat, MojganPrivalov, Timofei
By organisation
Department of Organic Chemistry
In the same journal
Journal of Chemical Physics
Chemical SciencesPhysical Sciences

Search outside of DiVA

GoogleGoogle Scholar

doi
pubmed
urn-nbn

Altmetric score

doi
pubmed
urn-nbn
Total: 2 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf