J. Iran. Chem. Soc., Vol. 8, No. 2 June 2011, pp.424~432.

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Transient Violation of Le Chatelier’s Principle for a Network of Water Molecules

P. Dasmeha,†, D. Ajlooa,* and D.J. Searlesb

aLaboratory of Computational Biophysical Chemistry, School of Chemistry,
Damghan University of Basic Sciences, Damghan, Iran
bQueensland Micro- and Nanotechnology Centre and School of Biomolecular
and Physical Sciences, Griffith University, Brisbane, Qld 4111, Australia             Present address: Department of Chemistry, Technical University of Denmark, Kgs. Lyngby, 2800, Denmark

     For a process in a small chemical system observed for short periods of time, the probability that it proceeds in the opposite direction to that found in the thermodynamic limit can be significant. We demonstrate this using simulations of a hydrogen-bonded network of water molecules whose temperature is changed from 300 K to 310 K.  It is shown that for this system, and finite periods (up to tenths of picoseconds), the change during an individual observation period might be in either direction which satisfies the transient fluctuation theorem for a temperature change (Journal of Chemical Physics, 131, 214503 (2009)).

Keywords: Le chatelier's principle, Fluctuation theorems, Small systems, Hydrogen-bond dynamics

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