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  • 1
    Electronic Resource
    Electronic Resource
    Direct laser excitation of triplet states in supersonic jets. Rotationally resolved 3Au .rarw. 1Ag excitation spectrum of glyoxal (1983)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 87 (1983), S. 4781-4783 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j150642a004
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  • 2
    Electronic Resource
    Electronic Resource
    Infrared-microwave double resonance and diode laser spectroscopy of the ν1/ν3 dyad of SnH4 (1989)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 2109-2114 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The interacting ν1 and ν3 bands of SnH4 have been studied by infrared absorption and infrared-microwave double resonance spectroscopy. The infrared spectrum has been taken with Doppler-limited resolution using a tunable diode laser. Pure rotational transitions within the ν3 state and rovibrational transitions between the ν1 and ν3 state have been observed by infrared-microwave double resonance. The infrared and microwave data have been fitted simultaneously to the ν1 and ν3 Hamiltonian coupled by one vibration–rotation interaction term. Seventeen spectroscopic constants have been determined for each of the five most abundant isotopic species.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.456004
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  • 3
    Electronic Resource
    Electronic Resource
    Anomalous band shifts in the 14 μm infrared absorption spectra of rare gas–BF3 complexes (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 4079-4087 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High resolution infrared absorption spectra of rare gas (Rg)–BF3 van der Waals complexes are studied in the 14 μm region near the ν2 band of BF3 monomer. Spectroscopic constants are determined for the 20Ne–11BF3, Ar–10,11BF3, 82–84,86Kr–11BF3, and 84Kr–10BF3 complexes. The observed redshifts from the monomer band origin correlate linearly with the rare gas polarizabilities. These shifts are about three times as large as those measured previously near the monomer ν3 band. This mode dependence of the shifts cannot be reproduced in a consistent manner with the instantaneous vibrational dipole–induced dipole interaction model, and indicates much greater enhancement of bonding energy by the excitation of ν2 vibration. The band shifts are discussed on the basis of electrostatic interaction between rare gas atom and point charges on BF3. The anomalous band shifts for the ν2 band are successfully accounted for by the interaction of vibrational dipole moment with the static induced dipole moment on the rare gas atom, which is parallel to the direction of vibrational motion. The isotope shifts observed for the Kr–BF3 complexes and the band shifts due to the modification of force field by vdW bonding are discussed with a linear triatomic molecular model.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.461863
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  • 4
    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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  • 5
    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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  • 6
    Electronic Resource
    Electronic Resource
    Free-jet infrared absorption spectroscopy of the C2H2–Ar complex in the doubly degenerate monomer C–H bending region (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 8385-8397 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Vibration–rotation transitions of the C2H2–Ar complex have been observed in the doubly degenerate monomer C–H bending (ν5) region via direct IR absorption of tunable diode laser radiation in a pulsed supersonic free jet. The spectrum is composed of in-plane and out-of-plane C–H bending bands, which are coupled with each other through a strong Coriolis interaction. Anomalous Coriolis coupling and A rotational constants indicates the failure in a semirigid-molecule description of this highly nonrigid system in the doubly degenerate bending manifold. A dynamical model calculation, where the large-amplitude van der Waals bending motion is treated as an internal rotation of the C2H2 monomer hindered by an anisotropic intermolecular potential, has revealed that the characteristic energy-level structure originates from its specific angular momentum coupling scheme involving an additional angular momentum for the intramolecular degenerate bending. The difference potential providing the parity doubling in the C–H bending manifold is estimated to be only about −0.1 cm−1.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.465614
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  • 7
    Electronic Resource
    Electronic Resource
    Dynamics of the oxygen combination reaction on Pt(111) initiated by photodissociation of N2O at 193 nm: O*+O(ad)→O2(g) (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 3143-3146 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The desorption of O2 is observed when a Pt(111) surface with the coadsorbates of oxygen atoms and N2O is irradiated with 193 nm photons. This indicates that an oxygen atom produced by photodissociation of N2O reacts with a chemisorbed oxygen adatom to form an oxygen molecule. The dynamics of the photoinitiated combination reaction of oxygen is studied by time-of-flight spectroscopy.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.465171
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  • 8
    Electronic Resource
    Electronic Resource
    Laser-induced photochemistry of methane on Pt(111): Excitation mechanism and dissociation dynamics (1996)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 4775-4788 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Adsorption states and photochemistry of methane and deuterated methane on a Pt(111) surface have been investigated by measuring temperature-programmed desorption spectra, x-ray photoelectron spectra, work function changes, and angle-resolved time-of-flight distributions of desorbed species. Methane weakly adsorbed on the Pt(111) surface at 40 K is dissociated to methyl and hydrogen fragments with laser irradiation at 193 nm. This is remarkably different from the photochemistry of methane in the gas phase where photodissociation takes place only at λ〈145 nm. While the photofragments mostly remain on the surface, some fraction of methyl desorbs with average translational energy of 0.27 eV. Photodesorption of methane is a minor channel. Desorbed methane is sharply collimated along the surface normal and shows two hyperthermal velocity components. Among the two, the faster component is attributed to associative recombination between a methyl adsorbate and a hydrogen atom produced by the photodissociation of adsorbed methane. The photochemical processes are substantially suppressed when the surface is covered with methyl adsorbate of 0.14 ML achieved by an extensive irradiation of 193-nm photons. In contrast, no photochemical reactions result from the 193-nm irradiation of methane adsorbed on a Xe/Pt(111) overlayer or from the 248-nm irradiation of methane on the bare Pt surface. These results indicate that the photochemical processes occur only for methane in close contact with substrate atoms under the irradiation of 193-nm photons. The incident angle dependence of cross sections of the photochemistry obtained with linearly polarized light indicates that direct electronic excitation of methane adsorbate plays an important role in the photochemistry of methane. The photochemistry of methane on Pt(111) at the wavelength substantially longer than that in the gas phase implies that the electronic excited state of methane is significantly mixed with substrate electronic states. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.472316
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  • 9
    Electronic Resource
    Electronic Resource
    Mechanism for the desorption of molecularly and dissociatively adsorbed methane on Pt(111) probed by pulse-laser heating (1996)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 5974-5982 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Dynamics of the thermal desorption of CD4 molecularly and dissociatively adsorbed on Pt(111) has been studied by laser-induced thermal desorption (LITD). CD4 adsorbates were prepared at the surface temperature of 55 K and the coadsorbates of CD3 and D were prepared by UV photolysis of CD4 adsorbates. The thermal desorption was induced by irradiating the surface with pulses of a frequency-doubled Nd:YAG laser and time-of-flight distributions of CD4 in each desorption channel were measured as a functions of the desorption angle (θ). The desorption of molecularly adsorbed CD4 shows a broad angular distribution (cos2.5 θ) and its translational energy distribution can be approximately described by the Maxwell–Boltzmann distribution with the temperature close to the estimated maximum surface temperature. In contrast, associatively formed CD4 desorbs sharply along the surface normal (cos31 θ) and its average translational energy is almost constant at 0.43 eV in the range of θ=0°–25°. The experimental results are compared with the calculated ones obtained from the statistical model developed by Ukraintsev and Harrison [J. Chem Phys. 101, 1564 (1994)]. Although the statistical model apparently succeeds in describing some of adsorption/desorption features by fitting the data of sticking coefficient measurements with molecular beams, it fails to predict the LITD data for the reverse process when their fitted data are applied in total. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.471329
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  • 10
    Electronic Resource
    Electronic Resource
    Erratum: Anomalous band shifts in the 14 μm infrared absorption spectra of rare gas–BF3 complexes [J. Chem. Phys. 96, 4079 (1992)] (1995)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 102 (1995), S. 7763-7763 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.469569
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