Vibrational Control in the Reaction of Methane with Atomic Chlorine

Kim, Zee Hwan; Bechtel, Hans A.; Zare, Richard N.

doi:10.1021/ja017180c

Cited by 88 publications

(64 citation statements)

References 19 publications

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“…When vibrationally non-adiabatic couplings are introduced, n 1 and n 3 differ in their ability to couple to lower energy vibrations, including the totally symmetric vibrational ground state, and thereby free vibrational energy for reaction coordinate motion. While similar patterns of mode-and bond selectivity were observed for methane activation on surfaces and for the gas phase bimolecular reaction of Cl with methane or its isotopologues, [69][70][71] the extent of bond-selectivity reported to date is greatest in gas-surface reactions. This most likely results from the extremely short surface residence times for methane, which severely limit the extent of IVR that can occur prior to the gasphase reagent's collision with the repulsive wall of the PES.…”

Section: Impact Of Ivr On Surface Reactivity and Dynamicssupporting

confidence: 62%

On the origin of mode- and bond-selectivity in vibrationally mediated reactions on surfaces

Killelea

Utz

2013

Phys. Chem. Chem. Phys.

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On the origin of mode-and bond-selectivity in vibrationally mediated reactions on surfaces. Physical Chemistry Chemical Physics, 15, 47: 20545-20554, 2013 The experimental observations of vibrational mode-and bond-selective chemistry at the gas-surface interface indicate that energy redistribution within the reaction complex is not statistical on the timescale of reaction. Such behavior is a key prerequisite for efforts to use selective vibrational excitation to control chemistry at the technologically important gas-surface interface. This paper outlines a framework for understanding the origin of non-statistical reactivity on surfaces. The model focuses on the kinetic competition between intramolecular vibrational energy redistribution (IVR) within the reaction complex, which in the long-time limit leads to statistical behavior, and quenching, scattering, or desorption processes that restrict the extent of IVR prior to reaction. Characteristic timescales for these processes drawn from studies of vibrational energy flow dynamics on surfaces and in the gas and condensed phases suggest that IVR is severely limited for important classes of surface reactions. Under these conditions, selective vibrational excitation can lead to preferential transition state access and result in mode-or bond-selective chemistry, even at high collision energies above the barrier to reaction. In addition to providing a basis for understanding experimental observations, the model provides guidance for identifying other gas-surface reactions that may exhibit mode-selective behavior.

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Section: Impact Of Ivr On Surface Reactivity and Dynamicssupporting

confidence: 62%

On the origin of mode- and bond-selectivity in vibrationally mediated reactions on surfaces

Killelea

Utz

2013

Phys. Chem. Chem. Phys.

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“…1, exciting a COH stretching eigenstate should carry the system over the barrier to cleave the COH bond to form the CH 2 D product, but exciting a COD stretching eigenstate should promote formation of the CH 3 product. Indeed, measurements find exactly that behavior in all of the substituted isotopologues, CH 3 D (37-40),CH 2 D 2 (41, 42), and CHD 3 (41,43), as illustrated by the results for CH 3 D shown in Fig. 2.…”

Section: Gas Phase Dynamics: Bimolecular Reactions Of Methane With Chsupporting

confidence: 60%

Chemical dynamics of vibrationally excited molecules: Controlling reactions in gases and on surfaces

Crim

2008

Proc. Natl. Acad. Sci. U.S.A.

180

141

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“…27 For example, the outcome of the reaction of CH 3 D with Cl-atoms could be controlled by vibrational excitation of the methane reagent. Preparation of CH 3 D in the first overtone of the C-D stretch vibration led exclusively to CH 3 + DCl products.…”

Section: Bond Selectivity In Gas-surface Reactionsmentioning

confidence: 99%

Quantum state resolved gas–surface reaction dynamics experiments: a tutorial review

Chadwick

Beck

2016

Chem. Soc. Rev.

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We present a tutorial review of our quantum state resolved experiments designed to study gas-surface reaction dynamics. The combination of a molecular beam, state specific reactant preparation by infrared laser pumping, and ultrahigh vacuum surface analysis techniques make it possible to study chemical reactivity at the gas-surface interface in unprecedented detail. We describe the experimental techniques used for state specific reactant preparation and for detection of surface bound reaction products developed in our laboratory. Using the example of the reaction of methane on Ni and Pt surfaces, we show how state resolved experiments uncovered clear evidence for vibrational mode specificity and bond selectivity, as well as steric effects in chemisorption reactions. The state resolved experimental data provides valuable benchmarks for comparison with theoretical models for gas-surface reactivity aiding in the development of a detailed microscopic understanding of chemical reactivity at the gas-surface interface. Key learning points(1) How to prepare beams of quantum state selected molecules through rapid adiabatic passage. (2) Physisorption vs. chemisorption. (3) What is state and mode specificity? (4) What is vibrational bond selectivity? (5) Orientation vs. alignment and alignment dependent reactivity.

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Vibrational Control in the Reaction of Methane with Atomic Chlorine

Cited by 88 publications

References 19 publications

On the origin of mode- and bond-selectivity in vibrationally mediated reactions on surfaces

On the origin of mode- and bond-selectivity in vibrationally mediated reactions on surfaces

Chemical dynamics of vibrationally excited molecules: Controlling reactions in gases and on surfaces

Quantum state resolved gas–surface reaction dynamics experiments: a tutorial review

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