The Infrared Spectrum of the Matrix-Isolated Phenyl Radical

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• 作者：Anders V. Friderichsen ; Juliusz G. Radziszewski ; Mark R. Nimlos ; Paul R. Winter ; David C. Dayton ; Donald E. David ; and G. Barney Ellison
• 刊名：Journal of the American Chemical Society
• 出版年：2001
• 出版时间：March 7, 2001
• 年：2001
• 卷：123
• 期：9
• 页码：1977 - 1988
• 全文大小：180K
• 年卷期：v.123,no.9(March 7, 2001)
• ISSN：1520-5126

文摘

We have measured the infrared absorption spectrum of C₆H₅, ²A₁, in an Ar matrix at 10 K. Theexperimental frequencies (cm^-1) and polarizations follow. a₁ modes: 3086, 3072, 3037, 1581, 1441, 1154,1027, 997, 976, 605; b₁ modes: 972, 874, 706, 657, 416; b₂ modes: 3071, 3060, 1624, 1432, 1321, 1283,1159, 1063, and 587. Three different methods have been used for the production of the phenyl radicals. Infraredabsorption spectra of five deuterated isotopomers, C₆D₅, p-C₆H₄D, p-C₆HD₄, o-C₆H₄D, and m-C₆H₄D, wererecorded to compare experimental frequency shifts with calculated (UB3LYP/cc-pVDZ) harmonic frequencyshifts. The use of CO₂ or NO as internal standards enabled the experimental determination of absolute infraredintensities. The linear dichroism was measured with photooriented samples to establish experimental polarizationsof each vibrational band. True gas-phase vibrational frequencies were estimated by considering the gas-to-matrix shifts and matrix inhomogeneous line broadening. The phenyl radical matrix frequencies listed aboveare within ±1% of the gas-phase vibrational frequencies. The C₆H₅ frequencies from this paper supersede ourearlier values reported in J. Am. Chem. Soc. 1996, 118, 7400-7401. See also: http://ellison.colorado.edu/phenyl.