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Liberation of H2 from (o-C6H4Me)3P-H(+) + (-)H(-)-B(p-C6F4H)3 ion-pair: A transition-state in the minimum energy path versus the transient species in Born-Oppenheimer molecular dynamics
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: 32017 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 147, no 1, article id 014303Article in journal (Refereed) Published
Abstract [en]

Using Born-Oppenheimer molecular dynamics (BOMD) with density functional theory, transition-state (TS) calculations, and the quantitative energy decomposition analysis (EDA), we examined the mechanism of H-2-liberation from LB-H(+) + H(-)-LA ion-pair, 1, in which the Lewis base (LB) is (o-C6H4Me)(3)P and the Lewis acid (LA) is B(p-C6F4H)(3). BOMD simulations indicate that the path of H-2 liberation from the ion-pair 1 goes via the short-lived transient species, LB center dot center dot center dot H(2 center dot center dot center dot)LA, which are structurally reminiscent of the TS-structure in the minimum-energy-path describing the reversible reaction between H-2 and (o-C6H4Me)(3)P/B(p-C6F4H)(3) frustrated Lewis pair (FLP). With electronic structure calculations performed on graphics processing units, our BOMD data-set covers more than 1 ns of evolution of the ion-pair 1 at temperature T approximate to 400 K. BOMD simulations produced H-2-recombination events with various durations of H-2 remaining fully recombined as a molecule within a LB/LA attractive pocket-from very short vibrational-time scale to time scales in the range of a few hundred femtoseconds. With the help of perturbational approach to trajectory-propagation over a saddle-area, we directly examined dynamics of H-2-liberation. Using EDA, we elucidated interactions between the cationic and anionic fragments in the ion-pair 1 and between the molecular fragments in the TS-structure. We have also considered a model that qualitatively takes into account the potential energy characteristics of H-H recombination and H-2-release plus inertia of molecular motion of the (o-C6H4Me)(3)P/B(p-C6F4H)(3) FLP.

Place, publisher, year, edition, pages
2017. Vol. 147, no 1, article id 014303
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Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-145795DOI: 10.1063/1.4989672ISI: 000405089400062PubMedID: 28688388OAI: oai:DiVA.org:su-145795DiVA, id: diva2:1137499
Available from: 2017-08-31 Created: 2017-08-31 Last updated: 2022-04-22Bibliographically approved

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Heshmat, MojganPrivalov, Timofei

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