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  • Elsevier  (222)
  • American Institute of Physics (AIP)  (22)
  • American Geophysical Union (AGU)
  • American Meteorological Society
  • Copernicus
  • 2000-2004  (99)
  • 1990-1994  (103)
  • 1975-1979  (53)
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  • 11
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 250-261 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: NH stretching overtone and combination states in HN3 X˜ 1A' were excited by IR–visible double resonance pumping and by direct overtone pumping in the range 6ν1 (17 670 cm−1) to 7ν1 (20 070 cm−1). NH fragments in the a 1Δ and X 3Σ− states were detected by laser induced fluorescence with sub-Doppler resolution to determine branching ratios, correlated fragment rotational state and kinetic energy distributions, and fragment vector correlations. The spin-forbidden triplet channel was accessible to all states excited, while the threshold for the singlet channel was determined to lie in the range 18 190 to 18 755 cm−1. The measured energy release places limits on the HN–NN bond energy, and the heights of barriers to reaction. The barrier in the singlet exit channel is at least 540 cm−1. The singlet channel accessed by 7ν1 dissociation is characterized by a Boltzmann-like NH rotational distribution (〈J NH〉≈3.5), highly excited N2 rotations (〈JN2〉 ≥ 20), and total translational energy release peaked away from zero (〈ET〉≈1350 cm−1). Vector correlations and Λ-doublet propensities indicate that nonplanar dissociation processes influence the NH rotations, but become less important for higher NH rotational states. The principal correlations are a strong positive recoil anisotropy (β≈0.6), a weak positive v–J correlation (βvJ≈0.17), and a JNH-dependent Λ-doublet propensity. A model using parent vibrational motion projected onto fragment rotation is suggested to explain these observations. The triplet channel exhibits similar NH and N2 rotational state distributions, with most of the available energy (substantially greater than in the singlet channel) appearing as fragment kinetic energy.
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  • 12
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 3536-3541 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The degree of vibrational excitation in the IBr fragment from the vibrational predissociation of NeIBr (A 3Π1) has been measured using two-color pump–probe laser-induced fluorescence spectroscopy. We find that for the lowest initial vibrational states examined, Δv=−1 dissociation pathways dominate the dynamics, while this channel is closed for v≥17. From this result, the A state binding energy (D0) of the complex is determined to be 67±4 cm−1, while that in the X electronic state is found to be 73±4 cm−1. The X state binding energy is identical to that for NeI2 and NeBr2, suggesting that the potential energy surface for NeIBr can be constructed from a summation of atom–atom pair potentials; we present such a model potential energy surface. The variations in the vibrational branching ratios, when combined with the trends in the predissociation rates, point to the importance of fragment rotational excitation in the dynamics of the dissociation.
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  • 13
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 2782-2789 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High-resolution spectra have been obtained for the predissociative N–H stretching overtone levels 5ν1 (15 120 cm−1) and 6ν1 (17 670 cm−1) of HN3, cooled in a free-jet expansion. The spectral bandwidth (Doppler limited at 0.007 cm−1 full width at half-maximum (FWHM) is sufficiently narrow to reveal the homogeneous linewidths of individual rovibrational transitions in the 6ν1 band, for which we previously measured the dissociation lifetime in time-domain experiments. Two distinct manifestations of vibrational coupling characterize the spectra: (a) anharmonic mixing of the N–H stretch with other vibrational motions to give a complex spectrum of vibrational eigenstates and (b) homogeneous widths of the resultant states determined by the dissociation lifetime. The results are discussed with reference to previous studies of overtone spectroscopy and intramolecular mixing. Time-domain measurements of dissociation rates are reported for four vibrational levels with zero-order labels 5ν1 +νx. Over the range 15 100 cm−1–17 700 cm−1, the dissociation rate increases monotonically with vibrational energy, with no apparent "mode-specific'' variations. This is interpreted in terms of the highly mixed character of any particular vibrational eigenstate that is excited.
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  • 14
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 5403-5418 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The vibrational dynamics of excited CO layers on Pt(111) were studied using infrared (IR) pump–probe methods. Resonant IR pulses of 0.7 ps duration strongly pumped the absorption line (ν≈2106 cm−1 ) of top-site CO. Weak probe pulses delayed a time tD after the pump were reflected from the CO-covered Pt(111) surface, and dispersed in a monochromator to determine the absorption spectrum of the vibrationally excited CO band, with time resolution 〈1 ps and monochromator resolution 〈1 cm−1. Transient spectra were obtained as a function of CO coverage, surface temperature, and laser fluence. Complex spectra for tD〈0 show features characteristic of a perturbed free induction decay, which are expected based on multiple-level density-matrix models. For tD≥0, the CO/Pt absorption exhibits a shift to lower frequency and an asymmetric broadening which are strongly dependent on fluence (1.3–15 mJ/cm2 ). Spectra return to equilibrium (unexcited) values within a few picoseconds. These transient spectral shifts and the time scale for relaxation do not depend (within experimental error) on coverage for 0.1≤aitch-thetaCO≤0.5 ML or on temperature for 150≤Ts≤300 K. A model for coupled anharmonic oscillators qualitatively explains the tD〉0 spectra in terms of a population-dependent decrease in frequency of the one-phonon band, as opposed to a transition involving a true CO(v=2) two-phonon bound state. The rapid relaxation time and its insensitivity to Ts and aitch-thetaCO are consistent with electron–hole pair generation as the dominant decay mechanism.
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  • 15
    Electronic Resource
    Electronic Resource
    New York, NY : American Institute of Physics (AIP)
    Physics of Fluids 3 (1991), S. 1461-1461 
    ISSN: 1089-7666
    Source: AIP Digital Archive
    Topics: Physics
    Notes: An experimental study was carried out to investigate turbulent mixing and entrainment across a density interface subjected to velocity shear. The flow configuration consisted of a salinity (stably) stratified two-fluid system with a driven upper turbulent layer and a quiescent lower layer. The experiments were performed in an Odell–Kovasznay tank and the mean flow in the upper layer was generated by using a conventional disk pump. The velocity and salinity measurements were made using a laser-Doppler anemometer and conductivity probes, respectively, and (quantitative) flow visualization was performed using the laser-induced fluorescence LIF technique. The refractive indices of upper and lower layers were matched, using salt and alcohol, to facilitate the use of laser-based flow diagnostic techniques. The measurements show that the rms velocity fluctuation u in bulk of the mixed layer scales well with the mean velocity jump Δu across the interface. The Thorpe, buoyancy, overturning, and integral length scales, as well as the maximum Thorpe displacement in the mixed layer, were also found to be proportional to the depth h of the upper mixed layer.The structure of the entrainment interface was found to depend strongly on the bulk Richardson number Ri (=Δb h/u2), where Δb is the buoyancy jump across the interfacial layer. At lower Ri, the entrainment occurred rapidly, as in a nonstratified fluid, but as Ri increases, the entrainment rate becomes a strong function of Ri: under the latter conditions, the interfacial wave breaking and Kelvin–Helmholtz instabilities were common features. At still higher Ri, the entrainment rate becomes vanishingly small and the interfacial mixing events were found to be controlled by the molecular diffusive effects. The measurement of the interfacial-layer thickness using LIF shows that it is much thinner than that measured using less-accurate techniques such as traversing probes. The nondimensional rms amplitude of the interfacial distortions at moderate and high Ri was found to be a strong function of Ri. The interfacial instabilities cause the formation of isolated mixing patches within the interface, which, when collapsed, form horizontal intrusions. The experimental measurements were in agreement with theoretical formulations based on scaling arguments.
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  • 16
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Review of Scientific Instruments 61 (1990), S. 2214-2219 
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: A high-power proportional temperature controller, using a fast infrared pyrometer, has been developed to change and control the temperature of metallic ribbon samples with microsecond response. The apparatus provides uniform and controlled heating for time-resolved x-ray scattering studies of structural phase transitions. When high-power pulse heating is used, the system is capable of increasing the sample temperature at rates in excess of 106 K/s, without overshoot and with subsequent control to ±1 K at temperatures as low as 650 K.
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  • 17
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Applied Physics Letters 80 (2002), S. 1809-1811 
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: We present in situ surface x-ray scattering measurements of PbTiO3 epitaxy by metal–organic chemical-vapor deposition. Oscillations in crystal truncation rod intensity corresponding to layer-by-layer growth are observed under a variety of growth conditions. At lower PbO overpressures, we observe a transition to step-flow growth and an increased rate of recovery after growth, indicating a higher surface mobility. © 2002 American Institute of Physics.
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  • 18
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: A technique for selective characterization of the structure of free and buried thin-film interfaces by vibrationally resonant sum frequency generation spectroscopy is described. Manipulation of Fresnel coefficients by choice of film thickness on a reflecting substrate allows simultaneous optimization of the signal from the desired interface and minimization of the signal from other interfacial sources. This technique is demonstrated for the free polystyrene (PS)/air and the buried PS/spin-on glass interfaces. Our spectra show that the pendant phenyl group orientation is similar at the buried and free interfaces, with the phenyls pointing away from the bulk PS at each interface.
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  • 19
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Applied Physics Letters 60 (1992), S. 2610-2612 
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: In situ surface x-ray scattering studies of the GaAs(001) surface were used to determine whether specific surface reconstructions occur during organometallic vapor-phase epitaxy. Prior to growth, we find that surfaces heated in the presence of As form a c(4×4) structure, while those heated in the absence of organometallics or in Ga form two similar fourfold reconstructions. We find no evidence for the presence of any surface reconstruction during the actual layer-by-layer growth process.
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  • 20
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 6262-6275 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The IBr fragment rotational state distributions that result when the NeIBr van der Waals molecule undergoes vibrational predissociation have been measured in a pump–probe laser-induced fluorescence experiment. Independent of initial vibrational state and the number of quanta of vibrational energy lost from the I–Br coordinate, the rotational distributions extend over the full range of energetically accessible states. From the observation of energetic constraints on the rotational distribution, the dissociation energy (D0) is calculated to be 65.5±1.2 cm−1 for the A electronic state, v=16. For the X electronic state, v=0, D0=71.8±1.2 cm−1. Quantum mechanical bound state calculations carried out on a model A electronic state potential energy surface are in quantitative agreement with this result. The rotational distributions are broader than that predicted by either a Franck–Condon or classical impulsive model for the dissociation. The distributions are qualitatively in accord with classical trajectory calculations. Analysis of specific rotational distributions in the context of the energy gap law shows poor quantitative agreement. The average fragment rotational energy relative to analogous Ne-containing complexes is, however, qualitatively predicted by the energy gap relations.
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