| Prediction of reaction barriers and force-induced instabilities under mechanochemical conditions with an approximate model: A case study of the ring opening of 1,3-cyclohexadiene. | |
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MedLine Citation:
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PMID: 22299856 Owner: NLM Status: In-Data-Review |
Abstract/OtherAbstract:
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Mechanochemistry, the use of mechanical stresses to activate chemical reactions, has emerged as a topic of significant interest. The present study examines the use of an approximate model for the prediction of reaction barriers under mechanochemical conditions using the ring opening of 1,3-cyclohexadiene along conrotatory and disrotatory directions as a specific test case. To do this, reaction barriers are evaluated using quantum chemical methods with an external force applied between various pairs of atoms. The results show that the consequent effects on the barrier exhibit a significant dependence on the locations of the atoms used to apply the external force, and in some cases, force-induced instabilities occur that alter the fundamental nature of the reaction pathway. The ability of an approximate model based on a second-order expansion of the force-modified potential energy with respect to nuclear coordinates to reproduce this behavior is then assessed. Good agreement between the results obtained through the quantum chemical calculations and approximate model is attained when force-induced instabilities do not occur. In addition, a strategy for predicting when such instabilities occur is presented and found to yield results that are in qualitative agreement with the quantum chemical calculations. Finally, the response of the system to the external force is interpreted in terms of the parameters entering the model, which correspond to interatomic distances and stiffnesses, and possibly sheds lights on ways to design molecules that exhibit a desired chemical response to mechanochemical conditions. |
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Authors:
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Adrian Bailey; Nicholas J Mosey |
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Publication Detail:
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Type: Journal Article |
Journal Detail:
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Title: The Journal of chemical physics Volume: 136 ISSN: 1089-7690 ISO Abbreviation: J Chem Phys Publication Date: 2012 Jan |
Date Detail:
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Created Date: 2012-02-03 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 0375360 Medline TA: J Chem Phys Country: United States |
Other Details:
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Languages: eng Pagination: 044102 Citation Subset: IM |
Affiliation:
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Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6, Canada. |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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