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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 6448-6459 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The dynamics of dissociation and negative ion formation have been investigated for the hyperthermal energy scattering of state-selected OCS+(X 2Πx, υ1, υ2, υ3) on Ag(111). Experiments reveal the effect that collision energy and internal energy have on the formation of scattered ionic products. An analysis of the appearance threshold and fragment velocity distribution for each scattered product channel [S−(2P), O−(2P), and SO−(X 2Π)] suggests that three distinct fragmentation mechanisms compete. Prompt impulsive dissociation of neutralized OCS+(X 2Π), followed by electron attachment to the nascent O fragment, is responsible for O−(2P) emergence. The production of SO−(X 2Π) relies on a collisionally activated distortion of OCS, forcing the O and S atoms close together while ejecting the central carbon atom. Finally, a comparison between the scattering of state-selected OCS+(X 2Πx, υ1, υ2, υ3) and S+(4S) on Ag(111) provides strong evidence that dissociative neutralization of OCS+(X 2Πx, υ1, υ2, υ3) leads to S−(2P) fragments. A discussion of time scales for the various dissociation mechanisms is presented. © 1997 American Institute of Physics.
    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. 5119-5122 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The reaction of 10–60 eV O+ ions with a silicon oxide thin film produces scattered O2−. Isotopic labeling experiments demonstrate that the O2− product is formed by an abstraction reaction and not by physical sputtering. Energy and angle resolved detection reveals a correlation between the scattered and incident particle momenta, indicative of a direct process in which the incoming oxygen atom reacts with an adsorbed oxygen atom through an Eley–Rideal mechanism. © 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 102 (1995), S. 4996-5011 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Hyperthermal energy reactions of NO+ with Ag(111) were studied as a function of collision energy and the incident diatom's internuclear-axis direction. Laser photoselection via (1+1') resonance enhanced multiphoton ionization (REMPI) prepared an aligned distribution of NO+(X 1Σ+, Etrans, v=0, J) prior to the molecules impact with the surface. The emergence of scattered O− products was enhanced when NO+ approached the surface with an "end-on'' rather than a "side-on'' orientation. Moreover, the magnitude of the reaction's alignment preference increased with decreasing collision energy. The appearance threshold for O− was approximately 20 eV. Classical trajectory calculations demonstrated that these results are consistent with a collision-induced dissociation mechanism mediated by both vibrational and rotational excitation upon impact. Reorientation of the internuclear axis during the collision drastically affects the simulated dissociation dynamics. No alignment preference for scattered NO− emergence could be discerned from the experiments. As a complement, the angular momentum mechanics are provided to predict the internuclear-axis distribution of ions created via two-photon REMPI. © 1995 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 85 (1986), S. 5457-5468 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A theory is presented to reduce 1+1 resonance enhanced multiphoton ionization (REMPI) spectra to accurate rovibrational state population distributions. Classical and quantum mechanical treatments are developed to model the polarization dependence of the REMPI signal from an initially aligned ground state having cylindrical symmetry. The theory includes the effects of saturation and intermediate state alignment. It is demonstrated that, for favorable cases, 1+1 REMPI allows the determination of the relative population as well as the quadrupole and hexadecapole moments of the alignment for rovibrational levels of a linear molecule. The classical treatment differs from that of the quantum treatment by less than 5% for rotational quantum numbers greater than J=4, suggesting that the classical treatment suffices for 1+1 REMPI in most molecular systems.
    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 85 (1986), S. 5469-5479 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A two-step methodology is presented for extracting ground state population distributions and alignment factors from 1+1 resonance enhanced multiphoton ionization (REMPI) spectra. In the first step the ion signal is corrected for variation with laser intensity as it is collected, generating an isopower spectrum. In the second step populations and alignments are derived from the isopower spectrum by correcting for the interdependent effects of saturation and intermediate state alignment. This procedure is applied to a room temperature thermal distribution of nitric oxide using the 1+1 REMPI process in which lines of the NO A 2Σ+–X 2Π (0,0) band constitute the resonant transition. The present treatment is able to recover the known rovibrational population distribution, independent of branch choice, over a wide range of practical operating conditions.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 9476-9479 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A hyperthermal beam of state-selected NO+ X Σ+(v=0–6) ions is scattered on a clean, well-characterized GaAs(110) surface. The threshold for the appearance of scattered O− ions occurs at a collision energy of 25 eV. Vibrational energy proves to be an order of magnitude more effective than translational energy in enhancing the yield in this channel.
    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 91 (1989), S. 3196-3207 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A model is presented to describe the dynamical processes of trapping/desorption as well as direct and indirect inelastic scattering on single-crystal surfaces. Newton's equations of motion are integrated for a system consisting of a rigid rotor interacting with a slab of 19 surface atoms. The surface atom which is closest to the center of mass of the molecule is permitted to translate only along the surface normal. In turn, this mobile surface atom is harmonically coupled to a microcanonical heat bath consisting of three subsurface atoms. This method is much less computationally intensive than the typical generalized Langevin equation (GLE) approach. Direct comparison is made between the predictions of this model and experiment for the NO/Pt(111) system. In the case of trapping/desorption, the model accurately describes the observed dependence of rotational alignment on rotational quantum number. For the inelastic scattering regime, the model successfully reproduces the degree of rotational excitation and qualitatively accounts for the observed rotational alignment. In addition, the model predicts correlations between final state velocity and final state rotational angular momentum (both direction and magnitude), as well as the effect of molecular orientation and surface impact parameter on the overall trapping probability.
    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 91 (1989), S. 3182-3195 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rotationally resolved experiments on the NO/Pt(111) system explore the mechanisms of inelastic scattering and trapping/desorption. The rotational dynamics associated with these two regimes are markedly different. A neat supersonic NO beam is scattered at normal incidence from a Pt(111) crystal at 375–475 K. The non-Boltzmann rotational population distribution of the scattered species exhibits considerable rotational excitation beyond the energy available from the incident beam. Thus, a surface vibration to rotational energy transfer mechanism must be operative. The accompanying rotational alignment data reveal that highly excited rotational states exhibit predominantly "cartwheel'' motion. In contrast, rotationally excited molecules that desorb from a 553 K Pt(111) surface show a preference for "helicopter'' motion. The opposite preferences for rotational alignment in the two dynamical regimes provide insight into the anisotropy of molecule–surface interactions.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 6791-6812 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The scattering of state-selected NO+(X 1Σ+, v=0–6) on GaAs(110) was explored across the hyperthermal energy region. Relative yields and velocity distributions for scattered anionic products NO−(X 3Σ−, v=0) and O−(2P) were measured as a function of the number of vibrational quanta and collision energy for NO+(X 1Σ+, v=0–6) incident on the surface. Facile neutralization along the inbound trajectory forms vibrationally excited NO(2Π) immediately prior to surface impact. Electron attachment to form NO−(X 3Σ−, v=0) occurs near the distance of closest approach between the molecule and surface. With regard to O−(2P) emergence, a collision-induced dissociation mechanism is consistent with the observed 25 eV threshold. Incident vibrational energy is as much as ten times more effective than translational energy in forming O−(2P). This paper represents the first experimental investigation into the effect of vibrational energy on electron transfer and dissociation of ions at surfaces and highlights the unique interplay between translational and vibrational motions in an ion/surface encounter.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5038-5039 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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