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  • American Institute of Physics (AIP)  (6)
  • 1
    Publication Date: 2016-08-05
    Description: In this work we seek to examine the nature of collisional energy transfer between HCl and Au(111) for nonreactive scattering events that sample geometries near the transition state for dissociative adsorption by varying both the vibrational and translational energy of the incident HCl molecules in the range near the dissociation barrier. Specifically, we report absolute vibrational excitation probabilities for HCl( v = 0 → 1) and HCl( v = 1 → 2) scattering from clean Au(111) as a function of surface temperature and incidence translational energy. The HCl( v = 2 → 3) channel could not be observed—presumably due to the onset of dissociation. The excitation probabilities can be decomposed into adiabatic and nonadiabatic contributions. We find that both contributions strongly increase with incidence vibrational state by a factor of 24 and 9, respectively. This suggests that V-T as well as V-EHP coupling can be enhanced near the transition state for dissociative adsorption at a metal surface. We also show that previously reported HCl( v = 0 → 1) excitation probabilities [Q. Ran et al. , Phys. Rev. Lett. 98 , 237601 (2007)]—50 times smaller than those reported here—were influenced by erroneous assignment of spectroscopic lines used in the data analysis.
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 2
    Publication Date: 2015-04-25
    Description: We report on the design and characterization of a new apparatus for performing quantum-state resolved surface scattering experiments. The apparatus combines optical state-specific molecule preparation with a compact hexapole and a Stark decelerator to prepare carrier gas-free pulses of quantum-state pure CO molecules with velocities controllable between 33 and 1000 m/s with extremely narrow velocity distributions. The ultrahigh vacuum surface scattering chamber includes homebuilt ion and electron detectors, a closed-cycle helium cooled single crystal sample mount capable of tuning surface temperature between 19 and 1337 K, a Kelvin probe for non-destructive work function measurements, a precision leak valve manifold for targeted adsorbate deposition, an inexpensive quadrupole mass spectrometer modified to perform high resolution temperature programmed desorption experiments and facilities to clean and characterize the surface.
    Print ISSN: 0034-6748
    Electronic ISSN: 1089-7623
    Topics: Electrical Engineering, Measurement and Control Technology , Physics
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  • 3
    Publication Date: 2015-10-01
    Description: We have constructed a potential energy surface (PES) for H-atoms interacting with fcc Au(111) based on fitting the analytic form of the energy from Effective Medium Theory (EMT) to ab initio energy values calculated with density functional theory. The fit used input from configurations of the H–Au system with Au atoms at their lattice positions as well as configurations with the Au atoms displaced from their lattice positions. It reproduces the energy, in full dimension , not only for the configurations used as input but also for a large number of additional configurations derived from ab initio molecular dynamics (AIMD) trajectories at finite temperature. Adiabatic molecular dynamics simulations on this PES reproduce the energy loss behavior of AIMD. EMT also provides expressions for the embedding electron density, which enabled us to develop a self-consistent approach to simulate nonadiabatic electron-hole pair excitation and their effect on the motion of the incident H-atoms. For H atoms with an energy of 2.7 eV colliding with Au, electron-hole pair excitation is by far the most important energy loss pathway, giving an average energy loss ≈3 times that of the adiabatic case. This increased energy loss enhances the probability of the H-atom remaining on or in the Au slab by a factor of 2. The most likely outcome for H-atoms that are not scattered also depends prodigiously on the energy transfer mechanism; for the nonadiabatic case, more than 50% of the H-atoms which do not scatter are adsorbed on the surface, while for the adiabatic case more than 50% pass entirely through the 4 layer simulation slab.
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 4
    Publication Date: 2014-09-25
    Description: We investigated the translational incidence energy ( E i ) and surface temperature ( T s ) dependence of CO vibrational excitation upon scattering from a clean Au(111) surface. We report absolute v = 0 → 1 excitation probabilities for E i between 0.16 and 0.84 eV and T s between 473 and 973 K. This is now only the second collision system where such comprehensive measurements are available – the first is NO on Au(111). For CO on Au(111), vibrational excitation occurs via direct inelastic scattering through electron hole pair mediated energy transfer – it is enhanced by incidence translation and the electronically non-adiabatic coupling is about 5 times weaker than in NO scattering from Au(111). Vibrational excitation via the trapping desorption channel dominates at E i = 0.16 eV and quickly disappears at higher E i .
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 5
    Publication Date: 2014-08-05
    Description: We present a new photo-fragment imaging spectrometer, which employs a movable repeller in a single field imaging geometry. This innovation offers two principal advantages. First, the optimal fields for velocity mapping can easily be achieved even using a large molecular beam diameter (5 mm); the velocity resolution (better than 1%) is sufficient to easily resolve photo-electron recoil in (2 + 1) resonant enhanced multiphoton ionization of N 2 photoproducts from N 2 O or from molecular beam cooled N 2 . Second, rapid changes between spatial imaging, velocity mapping, and slice imaging are straightforward. We demonstrate this technique's utility in a re-investigation of the photodissociation of N 2 O. Using a hot nozzle, we observe slice images that strongly depend on nozzle temperature. Our data indicate that in our hot nozzle expansion, only pure bending vibrations – (0, v 2 , 0) – are populated, as vibrational excitation in pure stretching or bend-stretch combination modes are quenched via collisional near-resonant V-V energy transfer to the nearly degenerate bending states. We derive vibrationally state resolved absolute absorption cross-sections for (0, v 2 ≤ 7, 0). These results agree well with previous work at lower values of v 2 , both experimental and theoretical. The dissociation energy of N 2 O with respect to the O( 1 D) + N 2 Σ g + 1 asymptote was determined to be 3.65 ± 0.02 eV.
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 6
    Publication Date: 2014-07-30
    Description: We observe a strong influence of molecular vibration and surface temperature on electron emission promoted by the de-excitation of metastable CO( a 3 Π) on a clean Au(111) surface using a molecular beam surface scattering apparatus. The de-excitation is independent of incidence translational energy. These observations appear incompatible with existing theories of metastable particle de-excitation on metal surfaces, which are based on the Auger effect. Instead, they strongly suggest a mechanism involving formation of a transient anion whose lifetime is similar to the vibrational period of the CO molecule.
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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