MICROWAVE AND INFRARED SPECTRA OF $C_{2}H_{4}--HCCH$
G. T. Fraser, Frank J. Lovas, R. D. Suenram, Jennifer Z. Gillies, C. W. Gillies
Abstract
G. T. Fraser, Frank J. Lovas, R. D. Suenram, Jennifer Z. Gillies, C. W. Gillies
Abstract
Microwave spectra of $C_{2}H_{4}--HCCH, C_{2}H_{4}--DCCH, C_{2}H_{4}--DCCD, D_{2}C=CH_{2}--HCCH$, and trans-HDC=CHD--HCCH have been recorded using a pulsed-nozzle Fourier-transform microwave spectrometer. An a-type, $\\bigtriangleup K_{a} = 0$ spectrum is observed, with a number of transitions being split into doublets due to tunneling. For the normal isotopic species we find A = 25981 (33) MHz, B+C = 3478.2560(13) MHz, and B-C = 89.45(18) MHz. The complex is shown to have a $C_{2v}$ structure in which the HCCH unit hydrogen bonds to the ethylene $\\pi$ cloud, with the HCCH axis normal to the plane of the ethylene. The hydrogen-bond length is found to be 2.78 {\\AA}. Centrifugal-distortion analysis yields a weak-bond stretching force constant of 0.025 mdyn/{\\AA}, corresponding to a stretching frequency of 56 $cm^{-1}$. Stark effect measurements determine the electric dipole moment of the complex to be 0.2654(6) D. An infrared spectrum of the asymmetric acetylenic C-H stretch in the complex has also been measured using an color-center laser optothermal spectrometer. The rotational lines are predissociation broadened, preventing the resolution of K structure. The Q-branch for the band overlaps the Q-branch for the equivalent band in the acetylene dimer.
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Microwave spectra of $C_{2}H_{4}--HCCH, C_{2}H_{4}--DCCH, C_{2}H_{4}--DCCD, D_{2}C=CH_{2}--HCCH$, and trans-HDC=CHD--HCCH have been recorded using a pulsed-nozzle Fourier-transform microwave spectrometer. An a-type, $\\bigtriangleup K_{a} = 0$ spectrum is observed, with a number of transitions being split into doublets due to tunneling. For the normal isotopic species we find A = 25981 (33) MHz, B+C = 3478.2560(13) MHz, and B-C = 89.45(18) MHz. The complex is shown to have a $C_{2v}$ structure in which the HCCH unit hydrogen bonds to the ethylene $\\pi$ cloud, with the HCCH axis normal to the plane of the ethylene. The hydrogen-bond length is found to be 2.78 {\\AA}. Centrifugal-distortion analysis yields a weak-bond stretching force constant of 0.025 mdyn/{\\AA}, corresponding to a stretching frequency of 56 $cm^{-1}$. Stark effect measurements determine the electric dipole moment of the complex to be 0.2654(6) D. An infrared spectrum of the asymmetric acetylenic C-H stretch in the complex has also been measured using an color-center laser optothermal spectrometer. The rotational lines are predissociation broadened, preventing the resolution of K structure. The Q-branch for the band overlaps the Q-branch for the equivalent band in the acetylene dimer.
Key concepts: Infrared, Microwave, Infrared spectroscopy, Spectral line, Materials science, Chemistry, Optics, Physics