title: Entropy from state probabilities: hydration entropy of cations.
abstract: Entropy is an important energetic quantity determining the progression of chemical processes. We propose a new approach to obtain hydration entropy directly from probability density functions in state space. We demonstrate the validity of our approach for a series of cations in aqueous solution. Extensive validation of simulation results was performed. Our approach does not make prior assumptions about the shape of the potential energy landscape and is capable of calculating accurate hydration entropy values. Sampling times in the low nanosecond range are sufficient for the investigated ionic systems. Although the presented strategy is at the moment limited to systems for which a scalar order parameter can be derived, this is not a principal limitation of the method. The strategy presented is applicable to any chemical system where sufficient sampling of conformational space is accessible, for example, by computer simulations.
authors: Department of Theoretical Chemistry, Faculty for Chemistry and Pharmacy, Center for Molecular Biosciences Innsbruck, Leopold-Franzens University Innsbruck, Innrain 80/82, A-6020 Innsbruck, Austria.
authors: Roland G
authors: RG
authors: Huber
authors: Julian E
authors: JE
authors: Fuchs
authors: Susanne
authors: S
authors: von Grafenstein
authors: Monika
authors: M
authors: Laner
authors: Hannes G
authors: HG
authors: Wallnoefer
authors: Nejma
authors: N
authors: Abdelkader
authors: Romano T
authors: RT
authors: Kroemer
authors: Klaus R
authors: KR
authors: Liedl
mesh_terms: D002412:Cations / Q000737:chemistry; D019277:Entropy; D008670:Metals / Q000737:chemistry; D056004:Molecular Dynamics Simulation; D014867:Water / Q000737:chemistry*
chemical_list: D002412:Cations; D008670:Metals; D014867:Water
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