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Title: Cooperative Roles of Charge Transfer and Dispersion Terms in Hydrogen-Bonded Networks of (H2O)n, n = 6, 11, and 16

The perturbation expansion based on the locally-projected molecular orbital (LPMO PT) was applied to the study of the hydrogenbonded networks of water clusters with up to 16 molecules. Utilizing the local nature of the occupied and excited MOs on each monomer, the chargetransfer and dispersion terms are evaluated for every pair of molecules. The two terms are strongly correlated with each other for the hydrogen-bonded pairs. The strength of the hydrogen bonds in the clusters is further classified by the types of the hydrogen donor and acceptor water molecules. The relative energies evaluated with th LPMO PT among the isomers of (H2O)6, (H2O)11, and (H2O)16 agree very well with those obtained from CCSD(T) calculations with large basis sets. The binding energy of the LPMO PT is approximately free of the basis set superposition errors caused both by the orbital basis inconsistency and by the configuration basis inconsistency.
Authors:
; ;
Publication Date:
OSTI Identifier:
1090169
Report Number(s):
PNNL-SA-95025
KC0301020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry A, 117(30):6641-6651
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English