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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 102 (1995), S. 2181-2186 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In this time-resolved study of vibrational dynamics of deuterated surface hydroxyls at acid sites in the zeolite Mordenite, we investigate the O–D T1 vibrational lifetime and transient band shifts. It is shown that after infrared excitation of the stretching mode of a surface hydroxyl, the excess energy is rapidly distributed over delocalized low-energy lattice modes upon de-excitation. This is asserted from the observation that nonexcited hydroxyls are perturbed by the relaxation of their excited counterparts immediately after this relaxation. This observation can be made owing to better resolution in transient transmission spectroscopy obtained by deuteration of the surface hydroxyls. This assignment allows for accurate estimates of lattice temperatures after relaxation of the vibration. Further, from the observation that the vibrational lifetime is dependent on frequency (increasing from 25 to 70 ps with increasing frequency), it is concluded that the deuterated acidic protons are hydrogen bonded to lattice oxygen atoms in the zeolite. © 1995 American Institute of Physics.
    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 103 (1995), S. 2661-2669 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have studied methanol at high pressure up to 33 GPa at room temperature with x-ray diffraction, optical (polarization) microscopy, Raman spectroscopy, and detection of hydrostaticity. A competition between crystallization and vitrification is observed when methanol is superpressed beyond the freezing pressure of 3.5 GPa: between 5.0 and 10.5 GPa crystals can nucleate, but if this region is surpassed quickly enough (within a few seconds), methanol remains amorphous. For the first time the nucleation rate and the crystal growth velocity have been studied as a function of pressure. These kinetic properties can be described by classical nucleation theory in agreement with, respectively, Turnbull–Fisher and Wilson–Frenkel type behavior using one and the same activated hard-sphere diffusion coefficient. The experimental nucleation rate and the crystal growth velocity are both effectively reduced to zero above 10.5 GPa, because the diffusion is suppressed. At these pressures methanol is compressed into a glass. © 1995 American Institute of Physics.
    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 104 (1996), S. 64-84 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: With two-color picosecond infrared laser spectroscopy the dynamics of O–H and O–D stretch vibrations in zeolites are investigated. Zeolites appear to be good model systems to study transfer of vibrational energy in a solid. For the O–D vibrations, transient spectral holes are burnt in the inhomogeneously broadened absorption bands by saturating the absorption with a strong pump pulse. From the spectral hole widths the homogeneous absorption linewidths are obtained. The excited population lifetimes are determined using a time-resolved pump–probe technique, and in combination with the homogeneous linewidth the pure dephasing time is revealed as well. For high concentrations of O–H oscillators the vibrational stretch excitations are found to diffuse spectrally through the inhomogeneous absorption band. This spectral diffusion process is explained by direct site-to-site transfer of the excitations due to dipole–dipole coupling (Förster transfer). The dependences of the transient spectral signals on oscillator concentration and the results of one-color polarization resolved experiments confirm this explanation. The spectral transients are satisfactorily described by simulations in which the site-to-site transfer by dipole–dipole coupling is taken into account. © 1996 American Institute of Physics.
    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 105 (1996), S. 3431-3442 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: With infrared transient hole-burning spectroscopy we have investigated the influence of OD⋅⋅⋅X hydrogen bonds on the vibrational line shape of O–D stretch vibrations in acid zeolites. The effect of hydrogen bonding on the line shape depends critically on the type of hydrogen bond. For hydrogen bonding in a rigid structure, the hydrogen bond determines the inhomogeneous linewidth, but the homogeneous linewidth is determined by coupling to a ∼200 cm−1 lattice mode as concluded from the temperature dependence of the dephasing rate. When the hydrogen bond is formed with an adsorbing molecule, the coupling between the high-frequency O–D stretch vibration and the low-frequency OD⋅⋅⋅X hydrogen-bond stretching mode does determine the homogeneous linewidth. The difference between the two systems can be explained by the different hydrogen-bond potentials. Variation of the adsorbate provides a means of obtaining conclusive information on the coupling mechanism between the high-frequency O–D stretching mode and the low-frequency OD⋅⋅⋅X hydrogen-bond stretching mode. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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