Chem. Rev. 1994, 94, 1975-1997
1975
Many-Body Effects in Intermolecular Forces Matthew J. Elrodt and Richard J. Saykally’ Department of Chemisfry, University of California, Berkeley, California 94720 Received January 27, 1994 (Revised Manuscript Received April 28, 1994)
Contents Introduction Experimental Methods Theoretical Methods Many-Body Effects in Atomic Systems Many-Body Effects in Molecular Systems A. Nonaqueous Systems B. Aqueous Systems VI. Conclusion
1975 1976 1977 1979 1988 1989 1990 1994
I. II. 111, IV. V.
1. Introduction The investigation of many-body effects in intermolecular interactions has assumed increasing prominence as modern experimental and computational technology has progressed such that a detailed description of the condensed phases of matter is now possible through computer simulations. Indeed, these technologies have recently allowed great advances in the understanding of the binary interaction, such that many relevant pair potential energy surfaces are now obtainable by inversion of experimental data or by direct a b initio quantum chemical calculation. Paralleling these developments, many workers have attempted to extend this success to the construction of more general many-body potential energy surfaces, which are ultimately necessary to achieve the goal of describing macroscopic properties from a rigorous microscopic viewpoint. Consider a system of N identical atoms; the total potential energy function V(rI,rz,...,r”N)is expanded as sum of n-body potentials: N
c c... N
v(r1,r2,...,rN)= c v z ( r i , r j )f i
