By A. G. Kalinichev, K. Heinzinger (auth.), Surendra K. Saxena (eds.)
ISBN-10: 1461228425
ISBN-13: 9781461228424
ISBN-10: 1461276926
ISBN-13: 9781461276920
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Sample text
At the same time, the gap between the first and second hydration shell begins to get filled up. In this way, the number of water molecules (six) in the first hydration shell of Li+ remains constant, as can be seen from nLiO(r = 3 A). The second hydration shell of Li+ almost disappears at high temperature and pressure. 5 A that slowly disappears with increasing distance. In the case of the iodide ion, the first hydration shell is, even at normal temperature and pressure, not well pronounced (lower part of Fig.
4 as dashed lines), suggesting that the critical point ofTIP4P water may lie about 50 to 70 degrees lower than the experimental one. The same conclusion can be drawn from the recently published data on the coexistence curve ofTIP4P water (De Pablo and Prausnitz, 1989). , 1990). The failure to reproduce critical parameters correctly seems to be a general feature of all empirical potentials, which are parameterized to describe the properties of water at liquidlike densities. The reason for this lies in the abovementioned effective nature of such potentials, which include only implicitly many-body effects.
12(a). As the TIP4P potential has been used, the only non-Coulombic contribution to the water-water interaction is the oxygen-oxygen Lennard-Jones term [Eq. (12)J and, hence, its contribution to (U(r» is both temperature- and density-independent [shown in Fig. 12(b) as a dotted lineJ. Therefore, in contrast to the BJE intermolecular potential, where changes with pressure in both Coulombic and non-Coulombic components of the average potential energy occur (Fig. 11), in the case of the TIP4P potential, only the change of the Coulombic part determines the differences between the (U(r» for different thermodynamic states.
Thermodynamic Data: Systematics and Estimation by A. G. Kalinichev, K. Heinzinger (auth.), Surendra K. Saxena (eds.)
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