The entropic and enthalpic contributions to force-dependent dissociation kinetics of the pyrophosphate bond

Matthew Hermes, Roman Boulatov

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

Abstract

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.

Original languageEnglish (US)
Pages (from-to)20044-20047
Number of pages4
JournalJournal of the American Chemical Society
Volume133
Issue number50
DOIs
StatePublished - Dec 21 2011

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