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  • 11
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 103 (1995), S. 5548-5553 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Isomerization of 2-vinylanthracene in the first excited singlet state has been studied over wide solvent-viscosity ranges. Steady-state and time-resolved fluorescence spectroscopy is used to determine the isomerization rate in compressed liquid solutions and in supercritical fluids. The "Kramers turnover,'' which indicates the transition of kinetics from "energy diffusion control'' regime to "spatial diffusion control'' regime, is clearly observed. The turnover behavior can be expressed by a single curve which bridges the two extremes by an additive form. The activation energy shift between the two extremes is 1.6 kJ/mol. Activation volumes at large viscosity in compressed liquid solutions are also discussed. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 592-599 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have measured the product state-selected differential cross-section (DCS), and the rotational angular momentum polarization, together with the energy distributions for the reaction O(1D)+N2O→NO+NO by utilizing Doppler-resolved polarization spectroscopy. The reaction dynamics of the vibrational channel forming the product NO(v′=0) is discussed based on both the scalar and vector properties. The product rotational and center-of-mass translational energy distributions are described as Boltzmann distributions with Trot(approximate)10 000 K and Ttr(approximate)13 000 K, respectively. These energy distributions are close to statistical predictions. The product DCS has substantial intensities over the whole angular range with a slight preference for backward scattering. The product rotational angular momentum vector j′ does not have a noticeable angular correlation with either k or k′ (the relative velocity vectors of the reactant and product, respectively). This nearly isotropic angular distribution of j′ indicates that both in-plane and out-of-plane motions of the collisional ONNO complex contribute to the product rotation to almost the same degree. Considering that this reaction has no potential well deep enough for the formation of a long-lived complex, these nearly statistical scalar and isotropic vector properties suggest that the energy redistribution among the internal modes of the collisional ONNO complex efficiently takes place. It implies that there are strong couplings among the internal modes. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 115-122 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The reaction of O(1D) with N2O produces two kinds of NO molecules, the "old" one which originally exists in N2O and the "new" one which includes the attacking O atom. Using the isotopically labeled reagent, we determined the vibrational state distributions of these NO's (X 2Π; v=0–17) separately. To obtain the distributions, two types of experiments were performed with the laser-induced fluorescence (LIF) technique via the NO A←X and B←X transitions. First, the relative populations of NO molecules (the sum of the two kinds of NO's) in v=0–11 levels were measured with unlabeled reagents. Then, isotopically labeled reaction, 18O(1D)+N2〈sup ARRANGE="STAGGER"〉16O→N18O+N16O, was utilized to determine the relative ratio between the two kinds of NO's in the vibrational levels of v=0–5 and 12–15. Combining the above results with previously determined vibrational state distribution of NO in high vibrational levels (v=11–17) [J. Chem. Soc., Faraday Trans. 94, 1575 (1998)], we were able to obtain a complete set of vibrational state distributions. It was found that the old NO dominantly populated in v=0 and 1 whereas the new NO extended its population toward higher vibrational levels (v=4–15). However, in high vibrational levels, the old NO still have a considerable population due to the rapid energy transfer to the old NO. The observed efficient energy transfer to the old NO is attributed to the absence of light atoms in the present reacting system. Compared with the system including hydrogen atoms, the state density and the momentum coupling among the vibrational modes are much larger and accelerate the energy redistribution in spite of the short lifetime. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 98 (1994), S. 2278-2281 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 15
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 98 (1994), S. 122-125 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 99 (1995), S. 13356-13361 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 17
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 99 (1995), S. 13652-13658 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 18
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 94 (1990), S. 6420-6425 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 19
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 7707-7716 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The state-selected differential cross section (DCS) and rotational angular momentum polarization for the reaction O(1D)+H2O→OH+OH have been measured by utilizing the polarized Doppler-resolved laser-induced fluorescence probing technique. Stereodynamics of the reaction channel forming the newly formed OH in the specific vibrational level v′=2 is discussed on the basis of the vector properties. A nearly isotropic DCS for the product OH(2Π3/2, v′=2, j′=5.5) most probably indicates that the reaction is dominated by an insertion mechanism involving a collisional HOOH complex with a lifetime comparable to its rotational period. The extremely asymmetrical energy partitioning between the two OH fragments, therefore, suggests that the redistribution of the available energy does not occur on a time scale comparable to the rotational period of the complex. Furthermore, it has been found that the product rotational angular momentum vector j′ is predominantly perpendicular to the collision plane spanned by k and k′ (the relative velocity vectors of the reactants and products, respectively) both for the forward- and backward-scattered products. It suggests that the initially excited bending motion of the H–O–O moiety in the collisional HOOH complex primarily contributes to the product rotation. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 20
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 9431-9436 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The effect of solvent shear viscosity on the formation of twisted intramolecular charge-transfer (TICT) state in the excited state for 4,4′-diaminodiphenyl sulfone (DAPS) in three linear alcohol solvents has been investigated by measuring the picosecond fluorescence lifetime as a function of pressure. At lower pressures the kinetics of the TICT-state formation is controlled by solvent relaxation. While with increasing pressure, the reaction path shifts toward the "high viscosity regime'' in which the reaction proceeds through the nonrelaxed path independent of solvent coordinate on the free energy surface of the S1 excited state. This behavior could be called as "pressure tuning effect'' of solvent viscosity. The power law parameter (α) is used as a measure of the viscosity dependence. For the high viscosity regime, α=0.2 can be attributed to the intrinsic viscosity dependence for barrier crossing. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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