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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 1698-1704 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The nondegenerate ν2←0 and 2ν2←ν2 bands of the ammonia cation NH+3 have been observed using tunable diode lasers combined with the velocity modulation technique. The ion was produced in a water-cooled 6 kHz ac glow discharge cell with a gas mixture of [He]@B:[N2]@B:[H2]=9@B:0.06@B:0.3 (Torr). From the observed spectra, the band origins were determined to be ν1←0=903.3898 cm−1 and ν2←1=939.771 cm−1. Vibration–rotation interaction constants and potential constants were derived. The missing of K=0 R-branch transitions with N=odd in the ν2←0 band and N=even in the 2ν2←ν2 band clearly shows the characteristics of a D3h planar structure with a 2A‘2 ground electronic state, just like its isoelectronic case CH3 radical. Spin–rotation doublets were well-resolved in R-branch transitions and spin–rotation interaction constants of the ground, ν2, and 2ν2 states were determined. A potential function consisting of a quadratic term and a quartic term was used for modeling the out-of-plane bending vibration of NH+3. In comparison with the methyl radical, the ammonia cation is more rigid and closer to a harmonic oscillator.
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  • 2
    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.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 979-982 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Infrared absorption in the 3 μm region of normal and ortho enriched solid deuterium samples at 4.2 K has been restudied with improved signal-to-noise ratio using a Bomem FTIR spectrometer. The zero-phonon U1←0(1) transition of deuterium was observed for the first time in the spectrum of normal D2. In addition, we also observed the phonon branches UR(0) [of the U1←0(0) transition] and UR(1) [of the U1←0(1) transition], which were not seen in previous work. The analysis of the spectra and the effect of p-D2 molecules on the intensities and linewidths of the transitions are discussed. The hexadecapole moment of the U1←0(0) transition was estimated to be 0.121 ea40 from the experimental integrated intensity.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 5882-5886 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Isotopic species of the HeH+ molecular ion provide an excellent testing ground for studying isotopic dependence of vibration–rotation constants because of the small masses of He and H isotopes. We have observed infrared spectra of the hot band v=2←1 of HeH+ and fundamental bands of isotopic species HeD+, 3HeH+, and 3HeD+, and obtained the Dunham coefficients Ykl, and the isotopically independent parameters Ukl, ΔHekl, and ΔHkl.
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  • 5
    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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  • 6
    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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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5644-5648 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Electric nuclear quadrupole hyperfine structure arising from a quadrupolar nucleus at the center of tetrahedral molecules, such as 189OsO4, is symmetry forbidden. However, through vibration–rotation distortion a small nuclear quadrupole coupling is induced. The hyperfine structure due to the vibrationally induced eqQ has been measured for a number of P- and R-branch transitions in the ν3 fundamental of 189OsO4, by using inverse Lamb dip spectroscopy. Microwave modulation sidebands of CO2 laser lines have been used as the tunable infrared radiation. From the analysis of the observed hyperfine structure patterns, the values of the scalar and tensor coupling constants have been determined to be χVs=−4.103±0.048 MHz and χVt=−3.090±0.059 MHz.
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  • 8
    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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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 6210-6215 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The overtone band of 2ν2(l=2)←0 of H+3 in the 2 μm infrared region has been observed in absorption by using a difference frequency laser spectrometer. The LiIO3 nonlinear optical system assembled by Bawendi and the bidirectional multiple path optical arrangement with velocity modulation have enabled us to observe 34 vibrational–rotation transitions from 5094 to 4557 cm−1. Liquid-N2 cooled plasmas were used for transitions involving low rotational levels, while gaseous-N2 cooled plasmas were used for high rotational levels, up to J,K=(9,9). From the relative intensities of the transitions, rotational temperature has been estimated to be ∼270 K for the former and ∼1300 K for the latter. The Δ||k−l||=±3 selection rule of the overtone band allows us to determine the absolute energy level values by combining the frequencies of the overtone band with those of the fundamental and hot bands.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 5282-5290 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The recent development of sub-Doppler spectroscopy using microwave modulation sidebands on CO2 laser radiation has enabled us to perform ultrahigh resolution tunable infrared spectroscopy and study the Stark and Zeeman effects in ethylene. Clear Stark splittings were observed in low J vibration–rotation transitions of the ν7 band by applying an electric field of up to 50 kV/cm. The Stark shift is caused by the polarizability of ethylene as well as by the second order Stark effect between the accidentally degenerate ν7 and ν8 vibrational states (ν07−ν08 =8.91 cm−1). Analysis of the observed Stark patterns gives the polarizability anisotropies for the ground state to be αaa− 1/2 (αbb+αcc) =1.91(13) A(ring)3 and αbb−αcc =0.07(19) A(ring)3 and for the ν7 state to be αaa− 1/2 (αbb+αcc) =1.78(11) A(ring)3 and αbb−αcc =0.15(14) A(ring)3. The dipole moment along the a axis of ethylene induced by the ν7 and ν8 vibrations was determined to be ∂2μa/∂q7 ∂q8 =0.0791(4) D. Zeeman splittings of ethylene in a magnetic field of approximately 2.5 kG were also observed. Since the infrared radiation was right-handed circularly polarized and the axial magnetic field was along the direction of the beam, only the Δm=+1 transitions were observed. The tensor components of the rotational g factors were determined to be gaa =−0.424(8), gbb =−0.123(8), and gcc =0.037(6). A qualitative discussion on the relationship of the electronic structure of ethylene and the rotational g factors is given.
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