Structures, energies, vibrational spectra, and electronic properties of water monomer to decamer

The correlation of various properties of water clusters (H2O)n=1–10 to the cluster size has been investigated using extensive ab initio calculations. Since the transition from two dimensional (2-D) (from the dimer to pentamer) to 3-D structures (for clusters larger than the hexamer) is reflected in the hexamer region, the hexamer can exist in a number of isoenergetic conformers. The wide-ranging zero-point vibrational effects of the water clusters having dangling H atoms on the conformational stability by the O–H flapping or proton tunneling through a small barrier (∼0.5 kcal/mol) between two different orientations of each dangling H atom are not large (∼0.1) kcal/mol). Large dipole moments (>2.5 D) are found in the dimer and decamer, and significant dipole moments (∼2 D) are observed in the monomer, hexamer, and nonamer. The polarization per unit monomer rapidly increases with an increasing size of the cluster. However, this increase tapers down beyond the tetramer. The O–H vibrational frequencies serve ...

[1]  T. Dunning,et al.  The structure of the water trimer from ab initio calculations , 1993 .

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

[3]  Jongseob Kim,et al.  Water dimer to pentamer with an excess electron: Ab initio study , 1999 .

[4]  Kwang Soo Kim,et al.  Harmonic vibrational frequencies of the water monomer and dimer: Comparison of various levels of ab initio theory , 1995 .

[5]  R. Knochenmuss,et al.  Structures and vibrational spectra of water clusters in the self-consistent-field approximation , 1992 .

[6]  V. Vaida,et al.  DIRECT ABSORPTION SPECTROSCOPY OF WATER CLUSTERS , 1999 .

[7]  Nauta,et al.  Nonequilibrium self-assembly of long chains of polar molecules in superfluid helium , 1999, Science.

[8]  H. Kwok,et al.  Infrared Vibrational Predissociation Spectroscopy of Water Clusters by the Crossed Laser-molecular Beam Technique , 1982 .

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

[10]  P. Cieplak,et al.  Ab initio study of intermolecular potential of H2O trimer , 1991 .

[11]  P. Kollman,et al.  Theory of the Hydrogen Bond: Electronic Structure and Properties of the Water Dimer , 1969 .

[12]  K. Jordan,et al.  Resonant ion-dip infrared spectroscopy of the S4 and D2d water octamers in benzene-(water)8 and benzene2-(water)8 , 1998 .

[13]  Hans Peter Lüthi,et al.  The MP2 limit correction applied to coupled cluster calculations of the electronic dissociation energies of the hydrogen fluoride and water dimers , 1999 .

[14]  F. B. van Duijneveldt,et al.  Convergence to the basis‐set limit in ab initio calculations at the correlated level on the water dimer , 1992 .

[15]  Sang Joo Lee,et al.  Benzene-hydrogen halide interactions: Theoretical studies of binding energies, vibrational frequencies, and equilibrium structures , 1998 .

[16]  B. Nelander,et al.  Infrared spectrum of the water dimer in solid nitrogen. I. Assignment and force constant calculations , 1977 .

[17]  D. Coker,et al.  The infrared predissociation spectra of water clusters , 1985 .

[18]  C. Sederholm,et al.  Correlation of Infrared Stretching Frequencies and Hydrogen Bond Distances in Crystals , 1956 .

[19]  Han Myoung Lee,et al.  STRUCTURES AND ENERGETICS OF THE WATER HEPTAMER : COMPARISON WITH THE WATER HEXAMER AND OCTAMER , 1999 .

[20]  Timothy S. Zwier,et al.  Resonant ion-dip infrared spectroscopy of benzene–H2O and benzene–HOD , 1995 .

[21]  Jongseob Kim,et al.  Structures, binding energies, and spectra of isoenergetic water hexamer clusters: Extensive ab initio studies , 1998 .

[22]  Entropy-driven structures of the water octamer , 1994 .

[23]  Nauta,et al.  Formation of cyclic water hexamer in liquid helium: the smallest piece of Ice , 2000, Science.

[24]  Roland Lindh,et al.  The water dimer interaction energy: Convergence to the basis set limit at the correlated level , 1997 .

[25]  T. Möller,et al.  Between vapor and ice: Free water clusters studied by core level spectroscopy , 1999 .

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

[27]  Kenneth D. Jordan,et al.  Binding energy of the ring form of (H2O)6: Comparison of the predictions of conventional and localized‐orbital MP2 calculations , 1996 .

[28]  C. J. Keoshian,et al.  QUANTITATIVE CHARACTERIZATION OF THE WATER TRIMER TORSIONAL MANIFOLD BY TERAHERTZ LASER SPECTROSCOPY AND THEORETICAL ANALYSIS. II. (H2O)3 , 1999 .

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

[30]  D. Wales,et al.  Theoretical study of the water tetramer , 1997 .

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

[32]  John S. Muenter,et al.  Microwave spectrum and structure of hydrogen bonded water dimer , 1974 .

[33]  Axel Kulcke,et al.  Infrared spectroscopy of small size‐selected water clusters , 1996 .

[34]  D. Clary,et al.  Characterization of a cage form of the water hexamer , 1996, Nature.

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

[36]  U. Buck,et al.  The asymmetric cage structure of (H2O)7 from a combined spectroscopic and computational study , 1999 .

[37]  D. Wales,et al.  Theoretical study of the water pentamer , 1996 .