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J. Chem. Phys. 136, 044102 (2012); http://dx.doi.org/10.1063/1.3678010 (11 pages)

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

Adrian Bailey and Nicholas J. Mosey

Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6, Canada

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(Received 5 August 2011; accepted 1 January 2012; published online 23 January 2012)

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.

© 2012 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. METHODOLOGY
  3. RESULTS
    1. Computational details
    2. Quantum chemical reaction barriers
    3. Evaluation of reaction barriers with Eq.
    4. Predicting force-induced instabilities
    5. Principles for mechanophore design
  4. CONCLUSIONS

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KEYWORDS and PACS

PACS

  • 82.20.Kh

    Potential energy surfaces for chemical reactions

ARTICLE DATA

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

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