Quantum-state-resolved reactivity of overtone excited CH 4 on Ni(111): Comparing experiment and theory

Hundt, P. Morten; van Reijzen, Maarten E.; Beck, Rainer D.; Guo, Han; Jackson, Bret

doi:10.1063/1.4975025

Title: Quantum-state-resolved reactivity of overtone excited CH ₄ on Ni(111): Comparing experiment and theory

Journal Article · Tue Feb 07 00:00:00 EST 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4975025· OSTI ID:1344086

Hundt, P. Morten ^[1]; van Reijzen, Maarten E. ^[1]; Beck, Rainer D. ^[1]; Guo, Han ^[2];

^[2]

Swiss Federal Institute of Technology in Lausanne (Switzerland). Lab of Molecular and Chemical Physics
Univ. of Massachusetts, Amherst, MA (United States). Dept. of Chemistry

Quantum state resolved reactivity measurements probe the role of vibrational symmetry on the vibrational activation of the dissociative chemisorption of CH₄ on Ni(111). IR-IR double resonance excitation in a molecular beam was used to prepare CH₄ in three different vibrational symmetry components A₁, E, and F₂ of the 2ν₃₂ antisymmetric stretch overtone vibration as well as in the ν1+ν3 symmetric plus antisymmetric C-H stretch combination band of F₂ symmetry. We measured the quantum state specific dissociation probability S₀ (sticking coefficient) for each of the four vibrational states by detecting chemisorbed carbon on Ni(111) as the product of CH₄ dissociation by Auger electron spectroscopy. We also observe strong mode specificity, where S₀ for the most reactive state ν₁+ν₃ is an order of magnitude higher than for the least reactive, more energetic 2ν₃-E state. Our first principles quantum scattering calculations show that as molecules in the ν1 state approach the surface, the vibrational amplitude becomes localized on the reacting C-H bond, making them very reactive. We found that this behavior results from the weakening of the reacting C-H bond as the molecule approaches the surface, decoupling its motion from the three non-reacting C-H stretches. Similarly, we find that overtone normal mode states with more ν₁ character are more reactive: S₀(2ν₁) > S₀(ν₁+ν₃) > S₀(2ν₃). The 2ν₃ eigenstates excited in the experiment can be written as linear combinations of these normal mode states. The highly reactive 2ν₁ and ν₁+ν₃ normal modes, being of A₁ and F₂ symmetry, can contribute to the 2ν₃-A₁ and 2ν₃-F₂ eigenstates, respectively, boosting their reactivity over the E component, which contains no ν₁ character due to symmetry.

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Research Organization:: Univ. of Massachusetts, Amherst, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-87ER13744

OSTI ID:: 1344086

Journal Information:: Journal of Chemical Physics, Vol. 146, Issue 5; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

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