Theoretical studies of geometric structures of phenol-water clusters and their infrared absorption spectra in the O–H stretching region

Abstract

Structure and vibrations of catechol and catecholH2O(D2O) in the S 0 and S 1 stateHigh resolution UV spectroscopy of phenol and the hydrogen bonded phenolwater cluster J. Chem. Phys. 104, 972 (1996); 10.1063/1.470821 Ab initio study of the structure of radical cations derived from Hbonded complexes: a comparison between [H2CO.H2O]+. and [H2CO.HF]+.The structures of the phenol-͑H 2 O͒ n clusters ͑nр4͒ are determined with ab initio molecular orbital methods, and their infrared spectra are calculated to analyze the experimental spectra reported in the preceding paper. The experimental infrared spectra of phenol-͑H 2 O͒ n clusters for nр4 have ''window regions,'' which are intervals of two types of OH stretching modes of the water molecules. The calculated IR spectra of isomers with a ring structure will reproduce these window regions. The ring is formed by a network of the hydration bonds of the ϪOH group of the phenol and water molecules. For nϭ4, two kinds of spectra are reported in the experiments. One spectrum has a window region similar to that of nр3. It is, therefore, identified to the isomers of a ring structure. The other one has several bands in the window region. The calculations for several isomers and large clusters suggest that this spectra might be attributed either ͑i͒ to the mixture of several branched isomers, ͑ii͒ to the products of evaporation of large clusters, or ͑iii͒ to the product of the proton transfer reaction in phenol-͑H 2 O͒ 4 cluster.

Hydrogen Bonding in Aromatic Alcohol-Water Clusters: A Brief Review

“…The phenol-(H 2 O) n clusters have been studied most intensively by many investigators [15][16][17][18][19][20][21][22] as the prototypical system for organic alcohol-water cluster. As depicted in Figure 1, the role of the OH group in the phenol-(H 2 O) n cluster can be either proton-donating or -accepting.…”

“…Therefore, systematic study on the hydrogen bond can reveal invaluable information for the structure and biochemical activity of protein. Since there are extremely many solvent molecules in the solution phase, however, it is more useful to study the hydrogen bonding in the clusters [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] consisting of a solute and a few solvent molecules.…”

Computational Study of Catechol-(H?O)?(n=1-3) Clusters

“…Detailed studies on the structures and IR frequencies were carried out for the phenol-(H 2 O) n clusters, up to n = 10. [10][11][12][13][14][15][16] Comparison of experimentally observed and theoretically predicted IR frequencies has given detailed information on the arrangement of water molecules around the hydroxyl and on the nature of hydrogen bonding. Depending on the number of water molecules, OH group in the phenyl ring acts either as proton donor or acceptor.…”

“…Since there are enormous number of solvent molecules in solution phase, they cannot explicitly be treated except by employing the approximations based on polarizable continuum model, 1,2 which is still being developed. Alternatively, the solution phase may be approximated as clusters, [3][4][5][6][7][8][9][10][11][12][13][14][15][16] in which a number of solvent molecules surround the solute to form a certain configuration. The properties of solution depending on the arrangement of solvent molecules around the solute may be efficiently studied by employing this approach.…”

Substituent Effects on the Binding Energies of Benzyl Alcohol-H2O Clusters: Ab initio Study

“…One approach to treat this situation is to employ the approximations based on polarizable continuum model, 1,2 in which the solvent is considered as continuum parametrized by bulk property such as the dielectric constant. Alternatively, the solution phase may be approximated as clusters, [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] when only a small number of solvents molecules affect the properties of solute. When a specific functional group of the solute interacts with solvent molecules, the cluster model may serve as good model system of the solution, since the interactions with the solvent molecules in the immediate vicinity of the functional group would largely determine the properties of the solution, while other solvent molecules may safely be considered as "spectators".…”