Perspectives on the reaction force constant |
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Authors: | Peter Politzer Jane S Murray Pablo Jaque |
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Institution: | 1. Department of Chemistry, University of New Orleans, New Orleans, LA, 70148, USA 2. CleveTheoComp, 1951 W. 26th Street, Suite 409, Cleveland, OH, 44113, USA 3. Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, Av. República 275, Santiago, Chile
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Abstract: | A synchronous, concerted chemical process is rigorously divided by the reaction force F(R), the negative gradient of V(R), into “reactant” and “product” regions which are dominated by structural changes and an intervening “transition” region which is electronically intensive. The reaction force constant κ(R), the second derivative of V(R), is negative throughout the transition region, not just at the nominal transition state, at which κ(R) has a minimum. This is consistent with experimental evidence that there is a transition region, not simply a specific point. We show graphically that significant nonsynchronicity in the process is associated with the development of a maximum of κ(R) in the transition region, which increases as the process becomes more nonsynchronous. (We speculate that for a nonconcerted process this maximum is actually positive.) Thus, κ(R) can serve as an indicator of the level of nonsynchronicity. Figure Profiles of potential energy V(R), reaction force F(R), and reaction force constant κ(R) along the intrinsic reaction coordinate R for a nonsynchronous concerted chemical reaction. |
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