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An improved thermodynamic perturbation theory for Mercedes-Benz water.

Urbic T, Vlachy V, Kalyuzhnyi YV, Dill KA

Faculty of Chemistry and Chemical Technology, University of Ljubljana, 1000 Ljubljana, Slovenia. tomaz.urbic@fkkt.uni-lj.si

We previously applied Wertheim's thermodynamic perturbation theory for associative fluids to the simple Mercedes-Benz model of water. We found that the theory reproduced well the physical properties of hot water, but was less successful in capturing the more structured hydrogen bonding that occurs in cold water. Here, we propose an improved version of the thermodynamic perturbation theory in which the effective density of the reference system is calculated self-consistently. The new theory is a significant improvement, giving good agreement with Monte Carlo simulations of the model, and predicting key anomalies of cold water, such as minima in the molar volume and large heat capacity, in addition to giving good agreement with the isothermal compressibility and thermal expansion coefficient.

Published 12 November 2007 in J Chem Phys, 127(17): 174511.
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