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  • 2000-2004  (23)
  • 1990-1994  (36)
  • 1
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 72 (1992), S. 2440-2448 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Photothermal laser ablation is studied using poly-(methyl methacrylate) films doped with a dye, IR-165, which functions as a molecular heater and thermometer. Direct optical measurements of temperature are performed on samples heated by 100 ns near-IR pulses at 1.064 μm, at rates dT/dt≈5×109 deg/s. Below ablation threshold, the heat capacity measured by optical calorimetry is precisely the value obtained by conventional calorimetry. At ablation threshold, the peak surface temperature is Tabl=600 °C. The increase in heat capacity observed above threshold, together with the results of a conventional thermal analysis, is used to determine the weight fraction of material decomposed at ablation time χth=0.02. With increasing pulse energy, the fraction decomposed increases and a more forceful ablation is observed, but the surface temperature does not continue to increase past Tlim=715 °C, which is determined to be the limiting temperature for thermal decomposition.
    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 92 (1990), S. 3798-3812 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A model and detailed calculations are presented to describe the flow of energy in a shocked solid consisting of large organic molecules. The shock excites the bulk phonons, which rapidly achieve a state of phonon equilibrium characterized by a phonon quasitemperature. The excess energy subsequently flows into the molecular vibrations, which are characterized by a vibrational quasitemperature. The multiphonon up pumping process occurs because of anharmonic coupling terms in the solid state potential surface. Of central importance are the lowest energy molecular vibrations, or "doorway'' modes, through which mechanical energy enters and leaves the molecules. Using realistic experimental parameters, it is found that the quasitemperature increase of the internal molecular vibrations and equilibration between the phonons and vibrations is achieved on the time scale of a few tens of picoseconds. A new mechanism is presented for the generation of "hot spots'' at defects. Defects are postulated to have somewhat greater anharmonic coupling, causing the vibrational temperature in defects to briefly overshoot the bulk. The influence of the higher defect vibrational temperature on chemical reactivity is calculated. It is shown that even small increases in defect anharmonic coupling have profound effects on the probability of shock induced chemistry. The anharmonic defect model predicts a size effect. The defect enhanced chemical reaction probability is reduced as the particle size is reduced.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 1825-1836 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ultrafast spectroscopy is used to investigate the temperature dependence of a bimolecular chemical reaction occurring at reaction centers embedded in a glycerol:water glass. The reaction centers consist of carbon monoxide bound to protoheme (PH–CO), or to myoglobin at pH=3 (Mb3–CO), a protein containing PH–CO with a broken proximal histidine–Fe bond. These systems have in common a small energetic barrier for rebinding of the photodissociated ligand. In the glass, the ligand is caged, so that only geminate rebinding is possible. Rebinding is not exponential in time. For t(approximately-greater-than)20 ps, the survival fraction of deligated heme N(t)∝t−n(n≥0). Below 100 K, rebinding is dominated by an inhomogeneous distribution of activation enthalpy P(ΔH
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 8771-8776 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The recombination after flash photolysis of carbon monoxide (CO) to protoheme (PH) in glycerol: water is studied over ten decades in time (1 ps to 10 ms). The rebinding consists of an initial nonexponential geminate phase followed by a slower exponential bimolecular phase. The entire time course of this reaction between 260 and 300 K can be explained in a unified way using a simple, analytically tractable diffusion model involving just three parameters: the relative diffusion constant, the contact radius, and the intrinsic rate of reaction at contact.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 1695-1710 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new method is presented for calculating ultrafast vibrational energy redistribution in anharmonic solids composed of large molecules. It is an improvement over the previous weak coupling model of Hill and Dlott [J. Chem. Phys. 89, 842 (1988)] because the emitted phonons are now allowed to act back on the excited vibrations. The model is used to investigate the dynamics of "ultrahot'' molecular solids, materials with enormous levels of vibrational or phonon excitation. Ultrahot solids are produced in laser ablation and shock-induced detonation. Using model parameters for crystalline naphthalene, we investigate multiphonon up pumping after a 40 kbar shock and vibrational cooling after strong excitation of a high frequency vibrational fundamental. In both processes, the phonons attain a state of internal equilibrium characterized by a time-dependent phonon quasitemperature θp(t) within a few ps. Energy redistribution among the phonons is efficient because phonons are more anharmonic than molecular vibrations. In up pumping, there is a large excess of phonons at t=0, which decreases as vibrations are pumped by phonons. Under these conditions, the rates of anharmonic scattering processes are maximum at t=0 and the lower levels of the ladder of molecular vibrations are pumped before the higher levels. The vibrational population distribution then rapidly attains an approximate state of quasiequilibrium, characterized by a vibrational quasitemperature θv(t). Thermal equilibrium where θp(t) = θv(t) is achieved in ∼100 ps. In vibrational cooling, there is initially a large excess of high frequency vibrations and few phonons. Because phonons accumulate as the vibrations cool, the rates of anharmonic scattering processes are a minimum at t=0. Under these conditions, the vibrations are far from a state of quasiequilibrium until thermal equilibrium is attained at ∼1 ns.
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  • 6
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 90 (2001), S. 5139-5146 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Shock-wave induced nanopore collapse (average diameter 100 nm) at 4.2 GPa in a 3-μm-thick poly-methyl methacrylate (PMMA) layer is measured in real time using coherent anti-Stokes Raman spectroscopy (CARS). Pore collapse is monitored via CARS transitions of a dye probe embedded in the porous medium. A pore collapse time constant of 3 ns in PMMA is in poor agreement with hydrodynamic pore collapse models but in excellent agreement with a viscoplastic model that uses the "shock viscosity" determined from the PMMA viscoelastic response to shock. The shock viscosity is more than 12 orders of magnitude smaller than the ordinary viscosity. A downstream gauge of polycrystalline anthracene monitors changes in the steeply rising shock front (〈25 ps rise time) after passing through the porous medium or a scattering medium with 100-nm-diam scatterers. The anthracene is a two-dimensional (2D) shock gauge that provides a time sequence of CARS spectra S(t,λ). The 2D gauge is shown to be capable of discriminating between a shock front that gradually rises with time constant tr or a bunch of steeply rising shocklets with an arrival time spread equal to tr. The transmitted shock front is shown to consist of a bunch of steep shocklets with an arrival time spread of 550 ps. © 2001 American Institute of Physics.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 8203-8209 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A molecular dynamics simulation of crystalline naphthalene is used to study nanometer scale thermal transport in solids. One molecule in a cluster of 75 is heated to a large initial temperature and then allowed to cool. Stochastic boundary conditions which preserve the time averaged volume of the cluster are used. The excess translational and librational energy of the hot molecule is lost within 1 ps. The excess vibrational energy is lost on the 100 ps time scale. Translational and librational energy propagates rapidly throughout the cluster at velocities which are comparable to the speed of sound. Despite the far slower rate of vibrational energy loss from the hot molecule, the growth of vibrational energy occurs uniformly on the other molecules in the cluster. Therefore intermolecular vibrational energy transfer occurs primarily via an indirect mechanism. Vibrational excitations are first converted into translational and librational excitations, which propagate throughout the cluster and then excite vibrations on distant molecules via multiphonon up pumping. Examination of the molecular neighbors shows that intermolecular transfer of mechanical energy can be anisotropic, since the hot molecule can only transfer energy where it contacts atoms on adjacent molecules. Energy transfer along the b- and c-crystallographic axes is more efficient than along the a axis. The most efficient energy transfer is in the direction of two of the four nearest neighbors. Transient hot spots are produced on these neighboring molecules. The implications of this anisotropic conduction for the propagation of thermal reactions, e.g., the decomposition of high explosives, are discussed briefly.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 4140-4151 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Optical calorimetry is used to study the dynamics of a polymer, poly-(methyl methylacrylate), (PMMA), subjected to a temperature jump which is faster than the time required for Boltzmann equilibrium. The temperature jump is produced by exciting a near-infrared dye embedded in the polymer with a 23 ps duration optical pulse. The magnitude of the temperature jump ΔT was as large as 125 degrees. To attain such a large temperature jump with good spatial uniformity requires optical heating pulses which strongly saturate the heater dye absorption. A formalism is developed to quantitatively treat optical heating with saturation. The heat capacity of the polymer, Cpol, can be determined to an accuracy of 8% using this method. The temperature jump data could not be fit by assuming the polymer heats up in a single stage. A quasitemperature model with two-stage heating, where the dye first excites polymer phonons and then the phonons excite polymer vibrations by multiphonon up pumping, gave quantitative agreement. The data at several values of ΔT were simultaneously fit using three adjustable parameters: κvc, the molecular thermal conductivity for vibrational cooling of the heater dye; κup, the molecular thermal conductivity for multiphonon up pumping; and Cpol. The value of κ vc was the same magnitude as κth, the thermal conductivity of the polymer, despite the fact that the vibrational cooling process occurs on the 1 nm length scale. The value of κup was 2 orders of magnitude smaller than κth.
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  • 9
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 75 (1994), S. 4975-4983 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: A large area shock target array was fabricated. By moving the array through a ps pulsed laser beam, shock waves could be reproducibly generated at a high repetition rate of up to ten shocks per second. The dynamics of shock wave propagation through various layers of the array were studied using optical nanogauges. A nanogauge is a sub micron thick layer whose optical properties are affected when the shock front passes through the layer. Since shock velocities are typically a few nm/ps, nanogauges can be used to study picosecond time scale shock dynamics. Using picosecond optical microscopy on targets with different thickness aluminum layers, it was found that the shock required 0.5 ns to form and then it propagated for a few ns with a constant velocity of 8.3 km/s (8.3 nm/ps), indicating a shock pressure of 49 GPa. The arrival time jitter of many hundreds of shocks, at an aluminum/polymer interface was found to be ±50 ps. The shock propagation through a polymer, polyester, was studied by observing the arrival of the front at a 50 nm thick nanogauge embedded in the polymer. When the shock was transmitted from the aluminum to a polymer layer, its velocity was 5.5 km/s, indicating a shock pressure of 14 GPa, in good agreement with shock impedance calculations. The shock target array is a flexible method of studying picosecond time scale dynamics of materials at and just behind the shock front. The use of different optical nanogauges, such as dye-doped polymer films, which can sense the temperature, pressure, and which indicate multiphonon up pumping, is briefly discussed.
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  • 10
    Electronic Resource
    Electronic Resource
    Woodbury, NY : American Institute of Physics (AIP)
    Applied Physics Letters 64 (1994), S. 715-717 
    ISSN: 1077-3118
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Multiplex picosecond time-resolved coherent anti-Stokes Raman spectroscopy (CARS) is used to study the dynamics of a thin film of a polymer, poly-methyl methacrylate (PMMA), undergoing photothermal laser ablation. Time-dependent CARS spectra of a PMMA Raman transition near 810 cm−1 reveal line broadening, attributed to temperature increase, peak shift, attributed to rapid volume expansion, and the appearance of a new peak attributed to the formation of methyl methacrylate by picosecond time scale polymer thermal decomposition. This is believed to be the first direct observation of a chemical reaction product in the solid itself, during laser ablation.
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