Chemical bonding in water clusters

Different sizes of water clusters from a dimer to twenty water molecules are studied using density functional theory. The binding energies of water clusters are calculated, and a relationship in terms of a simple function has been found between binding energy and the size of the water clusters. The interpolation of this correlation function reproduces the binding energies for the other water clusters to an accuracy within 1 kcal/mol. The extrapolation of the function gives the binding energy, −11.38 kcal/mol, which agrees very well with the experimental binding energy of ice, −11.35 kcal/mol. We also find small water clusters composed of mainly planar four membered rings to be more stable, implying the existence of magic numbers for water clusters with sizes of 4, 8, and 12.

[1]  Kwang Soo Kim,et al.  What is the global minimum energy structure of the water hexamer? The importance of nonadditive interactions , 1994 .

[2]  Axel D. Becke,et al.  Density-functional thermochemistry. I. The effect of the exchange-only gradient correction , 1992 .

[3]  Roger Hayward,et al.  The Hydrogen Bond , 1960 .

[4]  Kari Laasonen,et al.  Structures of small water clusters using gradient-corrected density functional theory , 1993 .

[5]  Walter Thiel,et al.  MNDO Study of Large Carbon Clusters , 1991 .

[6]  C. J. Tsai,et al.  Monte Carlo simulation of (H2O)8: Evidence for a low‐energy S4 structure and characterization of the solid ↔ liquid transition , 1991 .

[7]  C. J. Tsai,et al.  Theoretical study of the (H2O)6 cluster , 1993 .

[8]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[9]  R. Parr.  Density-functional theory of atoms and molecules , 1989 .

[10]  S. Farantos,et al.  Classical dynamics of hydrogen bonded systems : water clusters , 1993 .

[11]  Terry P. Lybrand,et al.  A new water potential including polarization: Application to gas‐phase, liquid, and crystal properties of water , 1990 .

[12]  E. Clementi,et al.  Revisiting small clusters of water molecules , 1986 .

[13]  Eduardo V. Ludeña,et al.  Energy Density Functional Theory of Many-Electron Systems , 1990 .

[14]  Walter Kauzmann,et al.  The Structure and Properties of Water , 1969 .

[15]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[16]  D. Wales,et al.  Rearrangements of model (H2O)8 and (H2O)20 clusters , 1993 .

[17]  C. E. Dykstra.  Structures and vibrational frequencies of small water complexes from electrical molecular mechanics , 1989 .

[18]  Larry A. Curtiss,et al.  Studies of molecular association in H2O and D2O vapors by measurement of thermal conductivity , 1979 .

[19]  C. E. Dykstra,et al.  Model studies of six-membered water clusters , 1992 .

[20]  Yang,et al.  Possible two-dimensional quasicrystal structures with a six-dimensional embedding space. , 1994, Physical review. B, Condensed matter.

[21]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[22]  Kwang Soo Kim,et al.  Ab initio studies of the water hexamer: near degenerate structures , 1991 .

[23]  Sotiris S. Xantheas,et al.  Ab initio studies of cyclic water clusters (H2O)n, n=1–6. II. Analysis of many‐body interactions , 1994 .

[24]  G. Fitzgerald,et al.  Structures of the water hexamer using density functional methods , 1994 .

[25]  Erich Wimmer,et al.  Density functional Gaussian‐type‐orbital approach to molecular geometries, vibrations, and reaction energies , 1992 .

[26]  Sotiris S. Xantheas,et al.  Ab initio studies of cyclic water clusters (H2O)n, n=1–6. I. Optimal structures and vibrational spectra , 1993 .