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Quantum effects on the maximum in density of water as described by the TIP4PQ/2005 model

Eva G. Noya, Carlos Vega, Luis M. Sesé, and Rafael Ramírez
Abstract

Path integral simulations have been performed to determine the temperature of the maximum in density of water of the rigid, nonpolarizable TIP4PQ/2005 model treating long range Coulombic forces with the reaction field method. A maximum in density is found at 280 K, just 3 K above the experimental value. In tritiated water the maximum occurs at a temperature about 12 K higher than in water, in reasonable agreement with the experimental result. Contrary to the usual assumption that the maximum in classical water is about 14 K above that in water, we found that for TIP4PQ/2005 this maximum is about 30 K above. For rigid water models the internal energy and the temperature of maximum density do not follow a linear behavior when plotted as a function of the inverse of the hydrogen mass. In addition, it is shown that, when used with Ewald sums, the TIP4PQ/2005 reproduces quite nicely not only the maximum in density of water, but also the liquid densities, the structure of liquid water and the vaporization enthalpy. It was shown in a previous work that it also reproduces reasonably well the density and relative stabilities of ices. Therefore the TIP4PQ/2005 model, while still simple, allows one to analyze the interplay between quantum effects related to atomic masses and intermolecular forces in water.