Ss. Xantheas, AB-INITIO STUDIES OF CYCLIC WATER CLUSTERS (H2O)(N), N=1-6 .2. ANALYSIS OF MANY-BODY INTERACTIONS, The Journal of chemical physics, 100(10), 1994, pp. 7523-7534
The magnitudes of the two- through six-body energy terms and their con
tribution to the interaction energy of small ring water clusters (n=2-
6) are computed at the Hartree-Fock (HF) and, second-through fourth-or
der many-body perturbation (MP2, MP4) levels of theory. The analysis i
s performed at the minimum energy geometries reported earlier [J. Chem
. Phys. 99, 8774 (1993)]. The correlation correction is found to accou
nt for a 10%-20% increase in the individual two-body terms and a much
larger increase of 75% for the three-body and 200% for the small four-
body terms. The MP4 results are found to differ only slightly (<2%) fr
om the corresponding MP2 results. We have found that three-body terms
have a significant contribution as high as 30% to the interaction ener
gy of the larger clusters and that four-body and higher order-terms ar
e negligible. The total and incremental association energies for;the p
rocesses n H2O-->(H2O)(n) and (H2O)(n-1) + H2O-->(H2O)(n), n=2-6 are a
lso reported.