Franks, Nicholas

Some most impressive computer simulations have been made in efforts to model the structure of liquid water. Yet, because these calculations usually are based on pair additivity of the potentials for the H-bonded water molecules, the possibility exists that subtle effects may escape the theoretician, as no means are provided to incorporate the possibility of extensive cooperativity—an aspect that Henry Frank (1972) has so eloquently stressed. Very likely, this is the crux of the problem of interfacially modified water if nothing else, the thermal anomalies (discussed below) in the properties of vicinal water strongly implicate cooperativity on a large scale—a collective behavior of water molecules that no existing potential function is able to reproduce. The cooperativity reflects nonpair additivity, and it does not seem plausible that effective potential energy functions can be devised that will remedy the specific lack of a detailed understanding of many-body interactions in water. Attempts to allow for cooperativity have been made by Finney, Barnes, and co-workers, notably Quinn and Nicholas (see Barnes et al., 1979). 

B. DORNER, J. M. OSTRESH, R. A. HOUGHTEN, RONALD FRANK, ANDREA TIEPOLD, JOHN E. FOX, ANDREW M. BRAY, NICHOLAS, J. EDE, IAN W. JAMES, and GEOFFREY WICKHAM... 

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