Observation of the π···H Hydrogen-Bonded Ternary Complex, (C2H4)2H2O, Using Matrix Isolation Infrared Spectroscopy
| Autor: | E Lewars, J. Mark Parnis, Matthew G. K. Thompson |
|---|---|
| Rok vydání: | 2005 |
| Předmět: |
Absorption spectroscopy
Hydrogen Matrix isolation Analytical chemistry Water chemistry.chemical_element Infrared spectroscopy Hydrogen Bonding Ethylenes Sensitivity and Specificity Vibration Models Chemical chemistry Spectroscopy Fourier Transform Infrared Quantum Theory Computer Simulation Physical and Theoretical Chemistry Fourier transform infrared spectroscopy Ternary complex |
| Zdroj: | The Journal of Physical Chemistry A. 109:9499-9506 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/jp053495t |
| Popis: | 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. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|