Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 136, Issue 3, Pages -Publisher
AIP Publishing
DOI: 10.1063/1.3677195
Keywords
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Funding
- European Community [MEST-CT-2005-020491]
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Activation parameters for the model oxidation half reaction of the classical aqueous ferrous ion are compared for different molecular simulation techniques. In particular, activation free energies are obtained from umbrella integration and Marcus theory based thermodynamic integration, which rely on the diabatic gap as the reaction coordinate. The latter method also assumes linear response, and both methods obtain the activation entropy and the activation energy from the temperature dependence of the activation free energy. In contrast, transition path sampling does not require knowledge of the reaction coordinate and directly yields the activation energy [C. Dellago and P. G. Bolhuis, Mol. Simul. 30, 795 (2004)]. Benchmark activation energies from transition path sampling agree within statistical uncertainty with activation energies obtained from standard techniques requiring knowledge of the reaction coordinate. In addition, it is found that the activation energy for this model system is significantly smaller than the activation free energy for the Marcus model, approximately half the value, implying an equally large entropy contribution. (C) 2012 American Institute of Physics. [doi:10.1063/1.3677195]
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