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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 4739-4747 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The vibrational and rotational state distribution was measured for NO produced from the reaction O(1D)+N2O→2NO via a reactant pair O(1D)⋅N2O, which, in turn, formed by the 193 nm photolysis of the N2O dimer. The dimer was generated by the supersonic expansion through a pulsed nozzle. The distribution was determined by using the laser-induced fluorescence of NO on its A–X transition. The rotational distribution was of the Boltzmann type characterized by a low temperature, 60–100 K, at each vibrational level measured. The vibrational distribution was found to be composed of the two components, one very cold and the other relatively hot. The experiment using an isotopically labeled N2O revealed that the vibrational energy was not equally distributed over two kinds of NO; the NO originally present in N2O was vibrationally cool while that formed from O(1D) and the terminal nitrogen of N2O was vibrationally hot. These results indicate that the reaction occurring is the abstraction of the terminal nitrogen by O(1D). The low rotational temperature, which sharply contrasts with the extremely high rotational excitation observed for the ordinary bimolecular reaction, can be rationalized by considering the geometrical difference in the encounter between the O(1D) atom and N2O. This fact, in turn, indicates that the product energy distribution is significantly affected by the orientation in the reactive encounter.
    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 113 (2000), S. 11109-11126 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The structure and excited state dynamics of jet-cooled 9,9′-bianthryl (BA) and its 1:1 van der Waals (vdW) complexes with Ne, Ar, and H2O were studied using rotational coherence spectroscopy (RCS). For a free BA molecule, the magnitude and persistence of the recurrent transient appearing in the time-correlated single photon counting (TCSPC) measurement was found to be dependent on the torsional level of BA, indicating the rotational constant changes with the torsional energy level. The RCS–TCSPC measurement of the BA–Ar and BA–H2O complexes in the S1 state showed no coherent transients. However, the pump–probe time-resolved fluorescence depletion (TRFD) detected the weak J-type transient. Those facts imply the loss of coherence in the BA vdW complexes due to the excited-state dynamics, which coincides with the analysis of the laser-induced fluorescence excitation and dispersed fluorescence spectra. The structure of the ground-state 1:1 BA complex with Ne, Ar, and H2O was determined based on the RCS transients observed in the TRFD measurement with the help of a minimum energy structure calculation using atom–atom pairwise potentials. The rapid dephasing in the excited state was demonstrated by the magic angle TRFD detection near t=0. The dominant dephasing process for the rare-gas complexes is ascribed to intramolecular vibrational energy redistribution (IVR) which is accelerated by significant coupling between the torsional vibration and the low-lying vdW vibrations. IVR process for the H2O complex accompanies the rapid conversion to the charge-transfer state, which is also responsible for the loss of excited-state coherence. © 2000 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 112 (2000), S. 8338-8346 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: State-selected differential cross sections (DCSs) have been measured for the OH radicals produced from the reactions of O(3P) with saturated hydrocarbons by utilizing Doppler-resolved polarization spectroscopy. Stereodynamics in the reactions of secondary (c-C6H12) and tertiary (i-C4H10) hydrogen atoms are discussed based on the dependences of the DCSs on the collision energy and the structure of these hydrocarbons. For the c-C6H12 reaction, the DCS of the OH(2Π3/2,v′=1,j′=3.5,A′) shows predominant intensities in the backward hemisphere with reference to the incident O(3P) atom at a mean collision energy of 〈Ecoll〉=12 kJ/mol. When the collision energy is raised to 〈Ecoll〉=33 kJ/mol, the OH radicals scattered in the forward hemisphere grow almost to match those in the backward hemisphere. The observed increase in the forward scattering implies that the collision energy makes the large impact parameter collisions contribute to the reactive scattering. At a similar collision energy of 〈Ecoll〉=31 kJ/mol the forward scattering component in the DCS of the i-C4H10 reaction does not exceed that of the c-C6H12. This shows that the cone of acceptance is not enlarged in the i-C4H10 reaction from that in the c-C6H12 reaction, as opposed to the expectation based on the height of activation barrier. The absence of the enlargement of the cone of acceptance can be attributed to a large steric hindrance caused by the three bulky methyl groups surrounding the reactive tertiary C–H bond of i-C4H10. The difference in the steric hindrance can explain the difference in the temperature-dependent pre-exponential factors of the macroscopic reaction rates between the abstraction of the secondary and tertiary C–H bonds. The collision energy dependence of the DCS as well as the internal excitation of alkyl radical products reveal that the O(3P)+alkane reactions are not always dominated by the simple rebound mechanism, which has long been believed. © 2000 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 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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  • 5
    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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  • 6
    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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  • 7
    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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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 7264-7272 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The nascent internal state distribution of NO(X 2Π) generated from the reaction, S(1D)+N2O→NO+NS, has been determined by utilizing the laser-induced fluorescence (LIF) technique. The average vibrational energy of NO relative to the statistically expected value is found to be 37%. This amount is obviously smaller than that of the fragment N 16O of the isovalent reaction 18O(1D)+N2 16O→N 18O+N 16O, though it is still larger than that of 18OH produced from the 16O(1D)+H2 18O reaction. To interpret the observed difference in the product energy partitioning, we have applied the quantal intramolecular vibrational-energy redistribution (IVR) representation to the energy mixing in the collision complex. Using a local-mode vibration model with momentum couplings, we have extracted the crucial factors determining the energy partitioning in these reactions. The reaction system consisting of only heavy mass atoms generally has a large vibrational coupling and a large density of states, both of which favor the rapid energy mixing during the short-lifetime of the intermediate complex. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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