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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 2385-2387 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Stimulated Raman excitation of (HCl)2 produces dimers with one quantum in the ν2 H–Cl stretch vibration. HCl fragments from predissociation of the dimers are detected by resonant multiphoton ionization (MPI). The HCl rotational state distribution shows a strong propensity to form the highest energetically accessible states.
    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 104 (1996), S. 2259-2270 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We describe a conceptually and experimentally simple approach for quantum-state-resolved measurement of the full three-dimensional recoil velocity distribution of the products from photodissociation or photoinitiated chemical reaction. The method uses pulsed lasers to determine two components of the recoil velocity vector, by spatial displacement of a probe laser beam relative to a photolysis laser beam, so we call this method POSTS, for position sensitive translational spectroscopy. The third component of the velocity vector is obtained from Doppler selection, ion time-of-flight mass spectrometry, spatial masking of a detector, or use of a one-dimensional array detector. POSTS requires only a single probe laser, and it is not essential that this laser have a narrow frequency bandwidth. Its TOF measurements can be made with very high resolution on a spatial scale as small as 0.1 cm. POSTS will work with all atomic and molecular species having any magnitude of recoil velocity, and with most pulsed-laser detection techniques. We demonstrate the capabilities of the POSTS method by velocity measurements on the H atoms from photodissociation of HI, and HCl molecules from the vibrational predissociation of (HCl)2. In the latter case the high resolution capabilities of POSTS allow a determination of the bond dissociation energy of the HCl dimer to an accuracy of ±1 cm−1 from TOF measurements on a spatial scale of only 0.1 cm. © 1996 American Institute of Physics.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 3055-3066 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A comprehensive study of the vibrational predissociation dynamics of the HCl dimer is reported. The predissociation lifetimes for three H–Cl stretch vibrationally excited states of (H35Cl)2 have been measured. Companion measurements for the H35Cl•H37Cl complex have also been made. These lifetimes range from 16(2) to 46(5) ns, lifetimes that are more than 106 times longer than the H–Cl stretch vibrational period. The correlated HCl(v′=0,j′)+HCl(v″=0,j″) fragment rotational state distributions have also been determined. These show a predominant dynamical bias that favors the production of j′,j″ pairs that maximize the rotational energy of the fragments and minimize their translational energy. The j′,j″ distribution is well described by a simple energy gap model of the dissociation. The results suggest a complex, for which there are substantial excursions from the equilibrium geometry, dissociation from a wide range of geometries, weak coupling of the H–Cl stretch vibrations to the dissociation coordinate, and a blurring of the distinction between hydrogen bonded and free HCl moieties. These results are consistent with theoretical studies of the HCl dimer potential energy surface. © 2000 American Institute of Physics.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 114 (2001), S. 7073-7080 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The rovibrational state distributions for the HCl product of the 193 nm photodissociation of (HCl)2, (HCl)2+hν→H+Cl+HCl, have been measured. The HCl dimer is prepared in a supersonic expansion of HCl in Ar, and its photoproduct detected by resonant multiphoton ionization under collisionless conditions. The state distributions are extremely "cold," with very little of the available energy deposited in either rotation or vibration of the surviving HCl molecule. Only v′=0 product is observed, and linear rotational surprisal analysis yields an extremely large surprisal parameter, θr′ of 95(8). The results are in excellent agreement with theoretical predictions. © 2001 American Institute of Physics.
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