Journal of Chemical Physics, Vol.100, No.2, 1589-1598, 1994
About the Nature of Intermolecular 3-Body Forces Ionic Systems - The Case of Protonated Hydrates
The three-body intermolecular energy is computed for the water/oxonium ion/water system from ab initio self-consistent-field (SCF) calculations and 170 geometrical configurations. It is decomposed into two parts : Delta E(nonadd)(1st) is obtained at the first iteration of the calculation and Delta E(nonadd)(deloc) is due to the following iterations till convergency The nonadditive three-body energy, E(nonadd)(ind), is computed from the perturbation theory. It is shown that all these energy components can be either attractive or repulsive according to the geometry. E(nonadd)(deloc) is often seriously different of E(nonadd)(ind), a nonadditive "induction-exchange" term being sometimes as large as E(nonadd)(ind). In most cases, this "induction-exchange" term is much larger than E(nonadd)(1st), with the same sign. This Suggests that these two terms can be approximated by a same expression, but because of the sign, more than one exponential term should be used. An approximation of E(nonadd)(ind) is discussed with a particular attention to the range of the validity according to the intermolecular distances.
Keywords:INTER-MOLECULAR INTERACTIONS;HARTREE-FOCK APPROXIMATION;MONTE-CARLO SIMULATION;1ST SOLVATION SHELL;LIQUID WATER;NON-ADDITIVITY;PERTURBATION-THEORY;HYDROGEN-BOND;POSITIVE-IONS;GAS-PHASE