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Jim J Lin

Publications and source records attributed to Jim J Lin.

11 recordsLinked to original sources

Crossed molecular beam studies on the reaction dynamics of O(1D)+N2O.

The reaction of oxygen atom in its first singlet excited state with nitrous oxide was investigated under the crossed molecular beam condition. This reaction has two major product channels, NO+NO and N2+O2. The product translational energy distributions and angular distributions of both channels were determined. Using oxygen-18 isotope labeled O(1D) reactant, the newly formed NO can be distinguished from the remaining NO that was contained in the reactant N2O. Both channels have asymmetric and forward-biased angular distributions, suggesting that there is no long-lived collision complex with lifetime longer than its rotational period. The translational energy release of the N2+O2 channel (fT = 0.57) is much higher than that of the NO+NO channel (fT = 0.31). The product energy partitioning into translational, rotational, and vibrational degrees of freedom is discussed to learn more about the reaction mechanism. The branching ratio between the two product channels was estimated. The 46N2O product of the isotope exchange channel, 18O+44N2O-->16O+46N2O, was below the detection limit and therefore, the upper limit of its yield was estimated to be 0.8%.

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Unimolecular dissociation of the propargyl radical intermediate of the CH+C2H2 and C+C2H3 reactions.

This paper examines the unimolecular dissociation of propargyl (HCCCH2) radicals over a range of internal energies to probe the CH+HCCH and C+C2H3 bimolecular reactions from the radical intermediate to products. The propargyl radical was produced by 157 nm photolysis of propargyl chloride in crossed laser-molecular beam scattering experiments. The H-loss and H2 elimination channels of the nascent propargyl radicals were observed. Detection of stable propargyl radicals gave an experimental determination of 71.5 (+5-10) kcal/mol as the lowest barrier to dissociation of the radical. This barrier is significantly lower than predictions for the lowest barrier to the radical's dissociation and also lower than calculated overall reaction enthalpies. Products from both H2+HCCC and H+C3H2 channels were detected at energies lower than what has been theoretically predicted. An HCl elimination channel and a minor C-H fission channel were also observed in the photolysis of propargyl chloride.

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State-correlation matrix of the product pair from F + CD(4)--> DF(nu') + CD(3)(0 v(2) 0 0).

The title reaction was investigated under crossed-beam conditions at three different collision energies, E(c) = 8.4, 2.76 and 1.46 kcal mol(-1). The combination of using a (2 + 1) resonance-enhanced multiphoton ionization for tagging state-specific CD(3) products and exploiting a time-sliced velocity imaging for ion detection allows us to reveal the coincident information of the two product pairs in a state-correlated manner. The pair-correlated results are reported for the two product vibrators -- (v(2) = 0, v'), (v(2) = 1, v'), (v(2) = 2, v') and (v(2) = 3, v')-and the dynamics attributes we examined include product state distributions, energy disposals and angular distributions. Together with our earlier communications, a rather complete picture of the correlated dynamics of the title reaction emerges. One of the major findings, the anti-correlated excitations of the two product vibrators at all four energies of this study, can qualitatively be understood by kinematics arguments.

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Rotationally selected product pair correlation: F+CD4 --> DF(nu')+CD3(nu2 = 0 and 2, N).

The product pair correlation of the title reaction was measured with rotational selection for both the vibrationally ground CD3(nu = 0) and umbrella-excited CD3(nu2 = 2) products. A striking linear relationship was found between the rotational energy of the selected CD3 product and the correlated kinetic energy release (or the average vibrational energy of the DF coproduct). Such a linearly correlated (or anticorrelated) dependence appears to be stronger for CD3(nu2 = 2,N) than for CD3(nu = 0,N). The mechanistic implication of the observation is that the rotational motion N of the CD3 product tends to lie antiparallel to the orbital angular momentum l' of the two departing products. The dependency on the K quantum number--the projection of N on the top axis--is, on the other hand, less significant yet noticeable.

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Unimolecular dissociation of the CH3OCO radical: an intermediate in the CH3O + CO reaction.

This work investigates the unimolecular dissociation of the methoxycarbonyl, CH(3)OCO, radical. Photolysis of methyl chloroformate at 193 nm produces nascent CH(3)OCO radicals with a distribution of internal energies, determined by the velocities of the momentum-matched Cl atoms, that spans the theoretically predicted barriers to the CH(3)O + CO and CH(3) + CO(2) product channels. Both electronic ground- and excited-state radicals undergo competitive dissociation to both product channels. The experimental product branching to CH(3) + CO(2) from the ground-state radical, about 70%, is orders of magnitude larger than Rice-Ramsperger-Kassel-Marcus (RRKM)-predicted branching, suggesting that previously calculated barriers to the CH(3)OCO --> CH(3) + CO(2) reaction are dramatically in error. Our electronic structure calculations reveal that the cis conformer of the transition state leading to the CH(3) + CO(2) product channel has a much lower barrier than the trans transition state. RRKM calculations using this cis transition state give product branching in agreement with the experimental branching. The data also suggest that our experiments produce a low-lying excited state of the CH(3)OCO radical and give an upper limit to its adiabatic excitation energy of 55 kcal/mol.

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Mode correlation of product pairs in the reaction OH+CD4-->HOD+CD3.

The hydrogen abstraction reaction from methane by a hydroxyl radical produces two polyatomic molecules. Each product has several vibrational modes that characterize distinct, concerted motions of the constituent atoms of the molecule. This communication describes the first measurement that maps out the coincident information on how the mode of excitation of one product varies with that of the other co-product. Such information on mode correlation of product pairs is particularly appealing in that it provides intuitively a glimpse of the reaction paths by which the chemical transformation occurs.

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Observation of a reactive resonance in the integral cross section of a six-atom reaction: F+CHD3.

The title reaction was investigated under crossed-beam conditions at collisional energies ranging from about 0.4 to 7.5 kcal/mol. Product velocity distributions were measured by a time-sliced, velocity-map imaging technique to explicitly account for the density-to-flux transformation factors. Both the state-resolved, pair-correlated excitation functions and vibrational branching ratios are presented for the two isotopic product channels. An intriguing resonance tunneling mechanism occurring near the reaction threshold for the HF+CD3 product channel is surmized, which echoes the reactive resonances found previously for the F+HD-->HF+D reaction and more recently for the F+CH4 reaction.

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Rotationally selected product pair correlation in F+CD(4)-->DF(nu('))+CD(3)(nu=0,N).

The title reaction was studied in a crossed-beam experiment by imaging of state-selected products. The rotational state selection of the CD(3) products was achieved using (2+1) resonance-enhanced multiphoton ionization. The coincident information on the DF coproducts was revealed in a state-resolved manner from time-sliced velocity map images. Significant dependences of both the correlated differential cross sections and the DF vibrational branching ratios on the "tagged" CD(3) rotation states were found. The dynamical implications of one of the major findings are discussed.

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Reactive resonance in a polyatomic reaction.

In the course of an extensive investigation aimed at understanding the detailed mechanisms of a prototypical polyatomic reaction, several remarkable observations were uncovered. To interpret these findings, we surmise the existence of a reactive resonance in this polyatomic reaction. The reaction of concern is F+CH4-->HF+CH3, and the abnormal attributes were revealed only near the reaction threshold. The discovery of reactive resonance in a polyatomic reaction is more than just an extension from a typical atom+diatom reaction. As shown here, it holds great promise to disentangle the elusive intramolecular vibrational dynamics of transient collision complex in the critical transition-state region.

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Imaging the pair-correlated excitation function: The F+CH4-->HF(v')+CH3(nu=0) reaction.

The velocity map ion imaging technique was applied to measure the reaction excitation function for the first time. It was found that the "raw" excitation function was significantly distorted by the density-to-flux transformation of the title reaction. Through a systematic investigation, possible reasons for such a dramatic effect are outlined. In addition, the state-resolved, pair-correlated excitation functions and branching ratios are presented. Effects of imperfect time slicing in the time-sliced velocity imaging technique in general are also discussed.

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State-specific correlation of coincident product pairs in the F + CD4 reaction.

When a chemical reaction forms two molecular products, even if the state-resolved differential cross section (DCS) for each product is obtained individually, the coincident attributes of the coproducts are still lacking. We exploit a method that provides coincidence information by measuring the state-resolved, pair-correlated DCS. Exemplified by the reaction F + CD4 --> DF + CD3, a time-sliced ion velocity imaging technique was used to measure the velocity distribution of a state-selected CD3 product and to reveal the information of the coincident DF in a state-correlated manner. The correlation of different product state pairs shows a striking difference, which opens up a new way to unravel the complexity of a polyatomic reaction.

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