Electronic origin of the dependence of hydrogen bond strengths on nearest-neighbor and next-nearest-neighbor hydrogen bonds in polyhedral water clusters (H ₂ O) _n , n = 8, 20 and 24

Journal Article · Fri Jan 01 00:00:00 EST 2016 · Physical Chemistry Chemical Physics. PCCP (Print)

DOI:https://doi.org/10.1039/C6CP02487D· OSTI ID:1290383

Iwata, Suehiro; Akase, Dai; Aida, Misako; Xantheas, Sotiris S.

The relative stability and the characteristics of the hydrogen bond networks in the cubic cages of (H2O)8, dodecahedral cages of (H2O)20,and tetrakaidodecahedral cages of (H2O)24 are studied. The charge-transfer and dispersion interaction terms of every pair of the hydrogen bonds are evaluated by using the perturbation theory based on the locally-projected molecular orbital (LPMO PT). Every water molecule and every hydrogen-bonded pair in polyhedral clusters are classified by the types of the adjacent molecules and hydrogen bonds. The relative binding energies among the polyhedral clusters are grouped by these classifications. The necessary condition for the stable conformers and the rules of the ordering of the relative stability among the isomers are derived from the analysis. The O–O distances and the pair-wise charge-transfer terms are dependent not only on the types of the hydrogen donor and acceptor waters but also on the types of the adjacent waters. This dependence is analyzed with Mulliken’s charge-transfer theory. The work is partially supported by the Grant-in-Aid for Science Research of JSPS (SI, DA, MA). SSX was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Battelle operates the Pacific Northwest National Laboratory for the US Department of Energy.

• Research Organization: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1290383
• Report Number(s): PNNL-SA-114206; KC0301050
• Journal Information: Physical Chemistry Chemical Physics. PCCP (Print), Vol. 18, Issue 29; ISSN 1463-9076
• Publisher: Royal Society of Chemistry
• Country of Publication: United States
• Language: English