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Theoretical Studies of Seemingly Simple Chemical Reactions
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry. (Theoretical Chemistry programme)
2013 (English)Licentiate thesis, comprehensive summary (Other academic)
Place, publisher, year, edition, pages
Uppsala universitet, 2013. , 38 p.
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-228291OAI: oai:DiVA.org:uu-228291DiVA: diva2:733493
Presentation
2013-12-11, Å80101, Uppsala University, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2014-07-15 Created: 2014-07-09 Last updated: 2015-03-24Bibliographically approved
List of papers
1. Mechanisms for the Breakdown of Halomethanes through Reactions with Ground-State Cyano Radicals
Open this publication in new window or tab >>Mechanisms for the Breakdown of Halomethanes through Reactions with Ground-State Cyano Radicals
2015 (English)In: ChemPhysChem, ISSN 1439-4235, E-ISSN 1439-7641, Vol. 16, no 1, 181-190 p.Article in journal (Refereed) Published
Abstract [en]

One route to break down halomethanes is through reactions with radical species. The capability of the artificial force-induced reaction algorithm to efficiently explore a large number of radical reaction pathways has been illustrated for reactions between haloalkanes (CX3Y; X=H, F; Y=Cl, Br) and ground-state (2Σ+) cyano radicals (CN). For CH3Cl+CN, 71 stationary points in eight different pathways have been located and, in agreement with experiment, the highest rate constant (108 s−1 M−1 at 298 K) is obtained for hydrogen abstraction. For CH3Br, the rate constants for hydrogen and halogen abstraction are similar (109 s−1 M−1), whereas replacing hydrogen with fluorine eliminates the hydrogen-abstraction route and decreases the rate constants for halogen abstraction by 2–3 orders of magnitude. The detailed mapping of stationary points allows accurate calculations of product distributions, and the encouraging rate constants should motivate future studies with other radicals.

Keyword
gas-phase reactions; quantum chemistry; radical reactions; reaction mechanisms; transition states
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:uu:diva-228448 (URN)10.1002/cphc.201402601 (DOI)000347239200018 ()25263486 (PubMedID)
Funder
Marcus and Amalia Wallenberg FoundationSwedish Research CouncilSwedish National Infrastructure for Computing (SNIC), p2011004
Available from: 2014-07-15 Created: 2014-07-15 Last updated: 2017-12-05Bibliographically approved
2. Ab initio quantum mechanical calculation of the reaction probability for the Cl- + PH2Cl -> ClPH2 + Cl- reaction
Open this publication in new window or tab >>Ab initio quantum mechanical calculation of the reaction probability for the Cl- + PH2Cl -> ClPH2 + Cl- reaction
2013 (English)In: Chemical Physics, ISSN 0301-0104, E-ISSN 1873-4421, Vol. 425, 134-140 p.Article in journal (Refereed) Published
Abstract [en]

The SN2 substitution reactions at phosphorus play a key role in organic and biological processes. Quantum molecular dynamics simulations have been performed to study the prototype reaction Cl-+PH2ClClPH2+Cl-, using one and two-dimensional models. A potential energy surface, showing an energy well for a transition complex, was generated using ab initio electronic structure calculations. The one-dimensional model is essentially reflection free, whereas the more realistic two-dimensional model displays involved resonance structures in the reaction probability. The reaction rate is almost two orders of magnitude smaller for the two-dimensional compared to the one-dimensional model. Energetic errors in the potential energy surface is estimated to affect the rate by only a factor of two. This shows that for these types of reactions it is more important to increase the dimensionality of the modeling than to increase the accuracy of the electronic structure calculation.

Place, publisher, year, edition, pages
Amsterdam: Elsevier, 2013
Keyword
Nucleophilic substitution (S(N)2); Reaction probability; Quantum dynamics
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:uu:diva-210368 (URN)10.1016/j.chemphys.2013.08.011 (DOI)000327443700016 ()
Funder
Marcus and Amalia Wallenberg FoundationSwedish National Infrastructure for Computing (SNIC), p2011004
Available from: 2013-11-06 Created: 2013-11-06 Last updated: 2017-12-06Bibliographically approved

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