title: Observation of the pi...H hydrogen-bonded ternary complex, (C(2)H(4))(2)H(2)O, using matrix isolation infrared spectroscopy.
abstract: FTIR absorption spectra of water-containing ethene:Ar matrices, with compositions of ethene up to 1:10 ethene:Ar, have been recorded. Systematically increasing the concentration of ethene reveals features in the spectra consistent with the known 1:1 ethene:water complex, which subsequently disappear on further increase in ethene concentration. At high concentrations of ethene, new features are observed at 3669 and 3585 cm(-1), which are red-shifted with respect to matrix-isolated nu(3) and nu(1) O-H stretching modes of water and the 1:1 ethene:water complex. These shifts are consistent with a pi...H interaction of a 2:1 ethene:water complex of the form (C(2)H(4)...H-O-H...C(2)H(4)). The analogous (C(2)D(4))(2)H(2)O complex shows little shifting from positions associated with (C(2)H(4))(2)H(2)O, while the (C(2)H(4))(2)D(2)O isotopomer shows large shifts to 2722.3 and 2617.2 cm(-1), having identical nu(3)(H(2)O)/nu(3)(D(2)O) and nu(1)(H(2)O)/nu(1)(D(2)O) values when compared with monomeric water isotopomers. Features at 3626.1 and 2666.2 cm(-1) are also observed and are attributed to (C(2)H(4))(2)HDO. DFT calculations at the B3LYP/6-311+G(d,p) level for each isotopomer are presented, and the predicted vibrational frequencies are directly compared with experimental values. The interaction energy for the formation of the 2:1 ethene:water complex from the 1:1 ethene:water complex is also presented.
authors.affiliation: Department of Chemistry, Queen's University, Kingston, Ontario, K7L 3N6, and Department of Chemistry, Trent University, Peterborough, Ontario, Canada, K9J 7B8. mthompso@trentu.ca
authors.forename: Matthew G K
authors.initials: MG
authors.lastname: Thompson
authors.forename: Errol G
authors.initials: EG
authors.lastname: Lewars
authors.forename: J Mark
authors.initials: JM
authors.lastname: Parnis
mesh_terms: D003198:Computer Simulation; D005030:Ethylenes / Q000737:chemistry*; D006860:Hydrogen Bonding; D008956:Models, Chemical; D011789:Quantum Theory; D012680:Sensitivity and Specificity; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D014732:Vibration; D014867:Water / Q000737:chemistry
chemical_list: D005030:Ethylenes; D014867:Water; C036216:ethylene