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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5139-5153 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The problem of classical vs nonclassical structure of protonated acetylene (vinyl cation) C2H+3 has been studied using high resolution infrared spectroscopy. The spectrum has been observed in the 3.2 μm region in air-cooled and water-cooled plasmas using C2H2:H2:He mixtures and in liquid nitrogen-cooled plasmas using CH4:H2:He mixtures. The difference frequency spectrometer with the velocity modulation method has been used to conduct the Doppler-limited, high sensitivity spectroscopy.The observed vibration–rotation pattern with the band origin at 3142.2 cm−1 has been identified as due to the antisymmetric CH stretching ν6 band of the C2H+3 ion with the nonclassical (bridged) structure. The observed spectral pattern was anomalous, but definitive assignments could be made for a part of the spectrum using the ground state combination differences which fit to the usual asymmetric rotor pattern. The discrimination between the classical and nonclassical structures is based on the observed spectral intensity pattern due to spin statistical weights. Agreement of vibrational band patterns and the rotational constants with ab initio values gives supporting evidence. The anomaly of the spectrum is at least partly ascribed to the small energy difference between the classical and nonclassical structures and possible rearrangement between them, the idea used by organic chemists over the years in wet chemistry. Systematic splittings with the intensity ratio of 2:1 have been noticed in some parts of the spectrum indicating that the protons tunnel between the apex and the two end equilibrium positions of the bridged structure. Using a simplified internal rotation model proposed by Hougen, the barrier height of the tunneling has been estimated. Chemical kinetics in plasmas related to C2H+3 is also discussed.We conclude that (1) the nonclassical structure is lower in energy than the classical structure, and (2) the apex proton and the two end protons exchange their positions with a measurable time scale.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 129-137 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The infrared spectrum of the A 2Πu←X 2∑+g electronic transition of C−2 has been observed under high resolution and analyzed. Three bands (v'←v)=(0,0), (1,1) and (0,1) have been observed; the first two bands were observed by using the difference laser frequency system in the frequency range of 3960–3780 cm−1 and the last by using a diode laser in the frequency range of 2210–2120 cm−1. A gas mixture of 50 mTorr of acetylene and 7 Torr of He was used for the ac discharge in an air-cooled and a water-cooled multiple inlet–outlet discharge tube. The simplicity of the optimum gas mixture suggested that C−2 is produced directly by simple dissociative electron attachment of acetylene. Altogether 103 absorption lines have been observed and accurately measured. Most of them are P, Q, and R form branches of allowed F1↔F1, F2↔F2 transitions although some forbidden F1↔F2 transitions and O and S transitions have also been measured. The hot bands (1,1) and (0,1) have been observed with intensity which is less than that for the (0,0) by a factor of only 2 or 3, in spite of the fact that the Franck–Condon factors of these transitions are lower than that for the (0,0) by 2.0 and 3.2, respectively, indicating that the vibrational temperature of C−2 in the He plasma is extremely high. All observed transitions are simultaneously fit to the formula for a 2Πu←2∑+g transition. The formulation of Brown and Watson has been used for the Hamiltonian for the 2Πu state. Molecular constants for C−2 in the two electronic states have been determined from the least-squares fitting. The constants are compared with those of other species isoelectronic to C−2. A short discussion is given about the astrophysical implication of the spectrum.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 666-678 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The infrared spectrum of the degenerate ν3 vibration–rotation band of methyl cation CH+3, one of the most fundamental carbo-ions, has been observed and analyzed. The spectrum was observed in the frequency range of 3240–2960 cm−1 using the difference frequency laser system as the tunable coherent infrared source. A gas mixture of He:H2:CH4∼700:20:1 with a total pressure of ∼7 Torr was used for the ac discharge in an air-cooled and a water-cooled multiple inlet–outlet discharge tube. The velocity modulation method together with noise subtraction and the unidirectional multiple passing of the beam was used for high sensitivity. The spectral lines of CH+3 appeared amid many other lines of C2H+2 and C2H+3 but their widths and their response to chemical conditions gave a good initial clue for the identification. Over 200 absorption lines have been assigned to CH+3 and the isotopic species 13CH+3. The spectral pattern clearly shows that the equilibrium molecular structure is a planar, equilateral triangle as expected from Herzberg's Rydberg spectrum of CH3 and from ab initio theory. The spectrum has been analyzed by using the symmetric rotor Hamiltonian in a degenerate vibrational state with various A1–A2 splittings and l resonance. The spectral lines have been least-squares fit with a standard deviation of 0.0058 cm−1, and led to 21 vibration–rotation constants of CH+3. Several analytical expressions have been derived among these constants to determine the structure and potential constants. Some perturbation has been noticed and discussed. Also quite a few lines which are definitely due to carbocations with one carbon atom have been left unassigned. The prominence of the CH+3 spectrum in hydrocarbon discharges confirms the importance of this species in the ion–molecule reaction scheme in the laboratory and in space which has already been noted by many people in the field. A simple discussion is given about the formation and destruction of CH+3 as well as other carbocations.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 3755-3756 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The infrared spectrum of the ν3 band of C2H+2(2Πu) has been observed and analyzed. This is the first observation of this fundamental molecular ion in any spectral range.
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  • 5
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 95 (1991), S. 2727-2732 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
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  • 6
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The infrared spectra of the band of the 2Π–2Π asymmetric hydrogen stretching vibration in the three isotopic acetylene ions C2H2+ (ν3), 13C2H2+ (ν3), and DCCH+ (ν1) have been observed and analyzed. The high resolution infrared spectra were recorded using a difference-frequency laser spectrometer as the tunable coherent infrared source probing an ac glow discharge. Velocity modulation, noise subtraction, and unidirectional multipassing of the infrared beam through the discharge cell provided high sensitivity. C2H2+ was produced in a gas mixture of H2, He, and either CH4 or C2H2, with a total pressure of ≈7 Torr in multiple-inlet–outlet air-, water-, and liquid-nitrogen-cooled discharge tubes; C2H2 freezing precluded its use in liquid-N2-cooled discharges. Complicated by a strong perturbation whose maximum occurred at N'=15 for F1 and N'=14 for F2, the assignment of the spectrum of normal C2H2+ was made possible by (1) fortuitous discharge conditions which provided unambiguous discrimination of C2H2+ lines from among concurrent CH3+ and C2H3+ lines, and (2) fitting the ground state combination differences. Sufficiently high N transitions were observed where Λ doubling was evident. The average bond lengths rz(CH)=1.077 (5) A(ring) and rz(CC)=1.257 (8) A(ring) were calculated from the spectroscopic constants determined from nonlinear least-squares fitting. Vibration–rotation interactions, the Renner–Teller interaction of perturbing states, plasma chemistry, and the relevance of the work in astrophysics are discussed.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 3476-3483 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The high resolution electronic spectrum of Ne⋅OH has been recorded in a supersonic free jet expansion using the laser-induced fluorescence technique. From an analysis of the spectrum which yields rotational constants, we are able to obtain Ne⋅OH bond lengths in several vibrational (hindered rotor) levels of the excited state and the vibrationless level of the ground state. We also measure the Fermi contact constant in the A˜ state which is, unlike Ar⋅OH, insignificantly perturbed from the value in the OH monomer. However, we now measure a parity doubling of the X˜ state rotational levels which is tenfold larger than the upper limit we established for such an interaction in Ar⋅OH. We interpret these latter measurements to imply weaker and more isotropic bonding in Ne⋅OH compared to Ar⋅OH in both electronic states.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 83 (1985), S. 3702-3703 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The vibration-rotation infrared spectrum of the ν3 fundamental band of the methyl cation CH+3 has been observed using a difference frequency laser system. The analysis of the spectrum demonstrates the D3h symmetry of the ion. This work marks the beginning of high resolution spectroscopy of simple polyatomic hydrocarbon cations.
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  • 9
    Publication Date: 1991-04-22
    Print ISSN: 0031-9007
    Electronic ISSN: 1079-7114
    Topics: Physics
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  • 10
    Publication Date: 1992-11-15
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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