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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 8380-8390 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The collisional deactivation of vibrationally highly excited azulene was studied from gas into compressed liquid phase by pump-and-probe picosecond laser spectroscopy. Collisional deactivation rates were compared with solvatochromic shifts Δν of the azulene S3←S0 absorption band under identical conditions. Employing supercritical fluids at pressures between 0.03 and 4000 bars and temperatures between 298 and 640 K, measurements covering the complete gas–liquid transition were performed. For the energy transfer experiments, azulene with an energy of ∼20000 cm−1 was generated by laser excitation into the S1- and internal conversion to the S0*-ground state. The subsequent loss of vibrational energy was monitored by following the transient absorption at the red wing of the S3←S0 absorption band near 290 nm. Transient signals were converted into energy-time profiles using hot band absorption coefficients from shock wave experiments for calibration and accounting for solvent shifts of the spectra. Under all conditions, the energy decays were found to be exponential with phenomenological deactivation rate constants kc. kc and spectral shifts Δν showed quite similar density dependences: the low pressure linear increase of both quantities with density ρ at higher densities starts to level off, before it finally becomes stronger again. The parallel behavior of energy transfer rate constants and solvent shifts becomes particularly apparent near to the critical point: measurements in propane at 3 K above the critical temperature showed that kc and Δν are essentially constant over a broad density interval near to the critical density. These observations suggest that both quantities are determined by the same local bath gas density around the azulene molecule. By Monte Carlo simulations it is shown that kc(ρ) follows an isolated binary collision (IBC) model, if the collision frequency Z is related to the radial distribution function g(r) of an attractive hard-sphere particle in a Lennard-Jones fluid. Within this model, average energies 〈ΔE〉 transferred per ethane–azulene collision are temperature independent between 298 and 640 K and pressure independent between 0.03 and 4000 bars. By means of radial distribution functions the density dependence of Δν can be represented as well. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The collisional deactivation of vibrationally highly excited azulene was studied from the gas to the compressed liquid phase. Employing supercritical fluids like He, Xe, CO2, and ethane at pressures of 6–4000 bar and temperatures ≥380 K, measurements over the complete gas–liquid transition were performed. Azulene with an energy of 18 000 cm−1 was generated by laser excitation into the S1 and internal conversion to the S0*-ground state. The subsequent loss of vibrational energy was monitored by transient absorption at the red edge of the S3←S0 absorption band near 290 nm. Transient signals were converted into energy-time profiles using hot band absorption coefficients from shock wave experiments for calibration and accounting for solvent shifts of the spectra. Under all conditions, the decays were monoexponential. At densities below 1 mol/l, collisional deactivation rates increased linearly with fluid density. Average energies 〈ΔE〉 transferred per collision agreed with data from dilute gas phase experiments. For Xe, CO2, and C2H6, the linear relation between cooling rate and diffusion coefficient scaled collision frequencies ZD turned over to a much weaker dependence at ZD(approximately-greater-than)0.3 ps−1. Up to collision frequencies of ZD=15 ps−1 this behavior can well be rationalized by a model employing an effective collision frequency related to the finite lifetime of collision complexes. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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