期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 133, 期 50, 页码 20044-20047出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja207421v
关键词
-
资金
- NSF [CHE-0748281]
We report quantum-chemical calculations of the activation free energy of solvolysis of the pyrophosphate bond in a conformationally flexible reactant coupled to a constraining potential. The results reveal a significant contribution of conformational entropy to the force-dependent kinetics of even a fairly small reactant, suggesting that accurate predictions or molecular interpretation of localized reaction kinetics in stretched polymers may require explicit consideration of their force-dependent conformational heterogeneity. We further show that modeling the conformational space of the reactant and the transition state as collections of overlapping harmonic wells accurately predicts the force-dependent activation free energy up to 2 nN without detailed quantum-chemical computations. An estimate of the activation energies is obtained from the minimal (Eyring Bell Evans) model using the local coordinate common to all nucleophilic displacement reactions.
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