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  • 1
    Electronic Resource
    Electronic Resource
    Pulsed-discharge-nozzle Fourier-transform microwave spectroscopy of HC3S(2Πr) and HC4S(2Πi) (1994)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 7342-7349 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rotational spectra of sulfur-bearing carbon-chain free radicals HC3S and HC4S have been observed for the first time by using a Fabry–Perot type Fourier-transform microwave spectrometer combined with a pulsed discharge nozzle. Rotationally cooled (∼1–2 K) HC3S(2Π1/2) and HC4S(2Π3/2) in their ground vibronic states have been produced by a discharge in a supersonic free jet of an Ar-diluted mixtures of C2H2 and CS2. Transitions of an isotopic species, HC334S, have also been observed in the same system, and those of DC3S and DC4S have been observed by using C2D2 instead of C2H2. The observed spectral patterns for these species have clearly indicated that HC3S and HC4S are linear free radicals in the ground electronic states with 2Π symmetry. The spectra of HC3S, HC334S, and DC3S have shown both the Λ-type doubling and the hyperfine splittings due to the H or D nucleus, whereas those of HC4S and DC4S have shown only the hyperfine splittings. The observed transition frequencies for the radicals in the 7–25 GHz region have been fitted to the Hamiltonian appropriate to 2Π electronic states, yielding the effective molecular constants including the hyperfine parameters. The total bond length of HC3S has been determined to be 5.107 A(ring) from the substituted-coordinate analysis.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.468292
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  • 2
    Electronic Resource
    Electronic Resource
    Photochemical hole burning of 1,4-dihydroxyanthraquinone in polymer glasses: Poly(ethylene), poly(methacrylic acid), and their copolymer systems (1988)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 1272-1278 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Photochemical hole spectra of 1,4-dihydroxyanthraquinone in polymer matrices at liquid helium temperatures were investigated by changing the main chain structure of polymer molecules systematically. Polymer molecules adopted here were poly(ethylene-co-methacrylic acid) (EMA) and its homopolymers poly(ethylene) (PE) and poly(methacrylic acid) (PMAA). Polarity of matrices or the number density of the electric dipoles mainly localized around the methacrylic acid units are decreased in the sequence of PMAA, EMA, and PE. Remarkable matrix effects on the hole-growth profiles were observed: The holewidth in the saturated regime decreased with decreasing the polarity of the polymer matrices from 1.4 cm−1 in PMAA through 0.15 cm−1 in EMA to 0.05 cm−1 in PE. The model of the photoinduced hole broadening is proposed in relation to the nature of two-level systems of the polymer glasses which exert influence on the holewidth. Dipole–dipole coupling is possibly a dominant interaction in the present systems. The results on the annealing properties of holewidth are also discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.454249
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  • 3
    Electronic Resource
    Electronic Resource
    Determination of the centrifugal–distortion-induced dipole moment of SnH4 by infrared–infrared double resonance Stark spectroscopy (1988)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 6747-6750 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Doppler-free infrared–infrared double resonance Stark spectrum is observed for SnH4 to determine the dipole moment induced by centrifugal distortion. A tunable diode laser is frequency modulated to generate sidebands for the double resonance. Twenty-eight double resonance signals are observed in 16 ν4 band absorption lines of the E symmetry species. The signals are assigned to the Δm=±2 resonances among first-order Stark multiplets in the ground and ν4 vibrational states. The induced dipole moment in the ground state is determined to be θxyz =4.26(12)×10−5 D from 12 signals observed in the J=5–17 rotational levels.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.454419
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  • 4
    Electronic Resource
    Electronic Resource
    Infrared–microwave double resonance and diode laser spectroscopy of the ν2/ν4 bands of SnH4 (1987)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5141-5148 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A pure rotational spectrum of SnH4 has been studied in the ν4 state by infared–microwave double resonance with a tunable diode laser. Twenty-seven double resonance signals have been observed for the 11 JJ–JJ type rotational transitions of the 5 Sn isotopic species. An infrared spectrum of the Coriolis-coupled ν2 and ν4 bands has been measured using a diode laser with Doppler-limited resolution. The ground-state scalar constants, B0, D0, and H0, have been determined by taking combination differences in the "forbidden'' ν2 band, which borrows intensity through a strong Coriolis interaction. The observed microwave and infrared data have been analyzed simultaneously by including the Coriolis interaction explicitly. More than 20 molecular constants have been determined accurately for the ν2/ν4 dyad of seven major isotopic species.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.453682
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  • 5
    Electronic Resource
    Electronic Resource
    Rotational spectra, structure, and intramolecular force field of the Hg–OCS van der Waals complex (1991)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 6989-6994 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Pure rotational spectra of the mercury–carbonyl sulfide complex have been observed by a pulsed-nozzle Fourier-transform microwave spectrometer, which has been recently constructed. The structure of the complex is found to be T-shaped, which is the same as the rare-gas–carbonyl sulfide complexes analogous to this system. The mercury–carbon distance and the Hg–C–O angle have been determined to be 3.7075(2) A(ring) and 86.98(1) deg, respectively, for 202Hg–OCS from the rotational constants. Harmonic force constants of the van der Waals modes have been derived by the centrifugal distortion constants. The electric quadrupole coupling constants for 201Hg–OCS have also been determined and the values indicate small perturbation on the electric charge distribution of the mercury atom by complex formation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.460232
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  • 6
    Electronic Resource
    Electronic Resource
    Rotational spectrum and internal rotation of a methane–HCl complex (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 6256-6265 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rotational spectra of CH4⋅HCl and CD4⋅HCl have been studied using a pulsed-nozzle Fourier-transform microwave spectrometer. The K=0 and K=1 components of the J=1–0,2–1, and 3–2 transitions have been detected in 4–18 GHz and assigned through the Cl-nuclear quadrupole hyperfine structure characteristic for a symmetric top. The Cl-isotopic dependence of the determined rotational constants is consistent with a methane...HCl geometry, i.e., methane acts as a proton acceptor and hydrogen chloride as a donor, respectively. The K=0 transitions were observed to be split into a doublet while only one component was detected for K=1. This anomaly has been explained as it is due to two-dimensional internal rotation of methane. An analysis considering the angular momentum coupling between the internal rotation and overall rotation of the complex gives a correlation between a free-internal rotor and a rigid symmetric top. The two observed K=0 and one observed K=1 components correspond to the three lowest states with different symmetries, A, F, and E, which correlate respectively to the j=0, 1, and 2 states of the freely rotating methane.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.458995
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  • 7
    Electronic Resource
    Electronic Resource
    Thermal electron attachment to carbon suboxide (1989)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 4148-4154 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Thermal electron attachment to C3O2 has been studied by the pulse radiolysis–microwave cavity technique. The time variation of electron concentration for mixtures C3O2 with Ar and N2 shows decays with two components and the profile changes significantly depending on both C3O2 and buffer-gas pressures. This can be interpreted by a fast electron attachment to C3O2 to form a compound negative ion in equilibrium with the free electron followed by a slow stabilization of the ion leading to a stable ion. Simulations for the observed decay profiles indicate the presence of two electron attachment–detachment equilibria, one associated with electron and C3O2 and the other including electron, C3O2, and the buffer-gas molecule. The slow stabilization occurs by two-step three-body processes involving intermediate dimer ion. This is supported by a "negative temperature dependence'' observed for the stabilization rates between 270 and 325 K. Though the electron affinity of C3O2 is negative, that of (C3O2)2 is likely to be positive. The role of electron attachment has been discussed in relation to an anomalously large cross section for ionization of a high-Rydberg atom by C3O2 reported previously.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.456844
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  • 8
    Electronic Resource
    Electronic Resource
    Free-jet infrared absorption spectroscopy of rare gas–11BF3 complexes in the 7 μm region (1989)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 7017-7021 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High-resolution infrared absorption spectra of the van der Waals complexes of BF3 with a rare gas atom (Ne, Ar, and Kr) are obtained near the ν3 band of BF3 monomer in a supersonic free jet. Each spectrum shows a characteristic perpendicular band of a symmetric-top molecule with C3v symmetry. The bands are shifted toward the red with respect to the monomer band by 0.3933(4), 1.7609(1), and 2.4059(4) cm−1 for NeBF3, ArBF3, and KrBF3, respectively. The Coriolis coupling constants of the complexes are almost identical to that of the monomer. These results show that complexing with a rare gas atom does not strongly influence the ν3 vibrational motion in BF3. The observed red shifts correlate well with the polarizabilities of the rare gas atoms. This finding is explained in terms of the instantaneous dipole–induced dipole interaction. The observed full widths of the Doppler-limited spectral lines, typically 70 MHz, indicate that the lower limit of the vibrational predissociation lifetime is 2 ns.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.456227
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  • 9
    Electronic Resource
    Electronic Resource
    Pure rotational spectrum of the mercury–argon van der Waals complex (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 3990-3991 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The pure rotational spectrum of the mercury–argon complex has been observed by pulsed-nozzle Fourier-transform microwave spectroscopy. Rotational constants, determined for six major isotopic species of mercury, fix the mercury–argon distance of 4.053 A(ring). The eQq constant for 201Hg⋅Ar is estimated to be less than 0.5 MHz and indicates small perturbation on the electric charge distribution of mercury when the complex is formed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.457810
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  • 10
    Electronic Resource
    Electronic Resource
    Mode-specific infrared photodissociation of nitric oxide dimers: High-resolution infrared spectroscopy of (14NO)2 and (15NO)2 (1990)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 937-942 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The high-resolution infrared absorption spectra of the symmetric (ν1) and the antisymmetric NO stretching (ν4) bands of nitric oxide dimer (NO)2 have been measured for 14NO and 15NO in supersonic free jets. The ν1 and ν4 bands exhibit a dramatic difference in linewidth: approximately 200 MHz [full width at half-maximum (FWHM)] for the ν1 band and approximately 5 GHz (FWHM) for the ν4 band. The predissociation lifetimes deduced from the linewidths are in excellent agreement with those reported in the recent time-resolved measurement for 14NO [Casassa et al., J. Chem. Phys. 89, 1966 (1988)]. There is no systematic dependence of the linewidth on the rotational states of (NO)2. Isotope substitution does not influence the linewidths significantly. However, the ν4 band structure of (15NO)2 is very different from that of (14NO)2, a difference that may be explained by a perturbation from a low-lying singlet vibronic state. All of the experimental results obtained to date may be accounted for if it is assumed that the predissociation of (NO)2 is enhanced by an electronically nonadiabatic transition to a repulsive triplet surface. Vibrational potential coupling between the NO stretching and intermolecular modes, particularly an in-plane NO bending mode, appears to play a key role in the mode specificity.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.458076
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