212 research outputs found
The determination of the infrared radiative lifetimes of a vibrationally excited neutral molecule using stimulated-emission-pumping, molecular-beam time-of-flight.
The authors present a new experimental method for measurement of collision-free infrared radiative lifetimes for single quantum states of a vibrationally excited sample. This method provides a more direct route to the infrared Einstein A coefficients than has been previously possible. Results for NO(X (2) Pi upsilon=21 and upsilon=7) are presented. Comparison to results of ab initio calculations shows excellent agreement. A controversy regarding the relative intensities of first overtone and fundamental emission intensities in NO is laid to rest. The most complete least squares analysis of existing data was carried out to derive the electric dipole moment function (EDMF) to an accuracy of +/-0.02 D between 0.9 and 1.7 Angstrom
Toward detection of electron-hole pair excitation in H-atom collisions with Au(111): Adiabatic molecular dynamics with a semi-empirical full-dimensional potential energy surface.
We report an analytic potential energy surface (PES) based on several hundred DFT energies for H interacting with a Au(111) surface. Effective medium theory is used to fit the DFT data, which were obtained for the Au atoms held at their equilibrium positions. This procedure also provides an adequate treatment of the PES for displacements of Au atoms that occur during scattering of H atoms. The fitted PES is compared to DFT energies obtained from ab initio molecular dynamics trajectories. We present molecular dynamics simulations of energy and angle resolved scattering probabilities at five incidence angles at an incidence energy, Ei = 5 eV, and at a surface temperature, TS = 10 K. Simple single bounce trajectories are important at all incidence conditions explored here. Double bounce events also make up a significant fraction of the scattering. A qualitative analysis of the double-bounce events reveals that most occur as collisions of an H-atom with two neighboring surface gold atoms. The energy losses observed are consistent with a simple binary collision model, transferring typically less than 150 meV to the solid per bounce
Improved setup for producing slow beams of cold molecules using a rotating nozzle
Intense beams of cold and slow molecules are produced by supersonic expansion
out of a rapidly rotating nozzle, as first demonstrated by Gupta and
Herschbach. An improved setup is presented that allows to accelerate or
decelerate cold atomic and molecular beams by up to 500 m/s. Technical
improvements are discussed and beam parameters are characterized by detailed
analysis of time of flight density distributions. The possibility of combining
this beam source with electrostatic fields for guiding polar molecules is
demonstrated
Adsorption and absorption energies of hydrogen with palladium
Thermal recombinative desorption rates of HD on Pd(111) and Pd(332) are reported from transient kinetic experiments performed between 523 and 1023 K. A detailed kinetic model accurately describes the competition between recombination of surface-adsorbed hydrogen and deuterium atoms and their diffusion into the bulk. By fitting the model to observed rates, we derive the dissociative adsorption energies (E0, adsH2 = 0.98 eV; E0, adsD2 = 1.00 eV; E0, adsHD = 0.99 eV) as well as the classical dissociative binding energy ϵads = 1.02 ± 0.03 eV, which provides a benchmark for electronic structure theory. In a similar way, we obtain the classical energy required to move an H or D atom from the surface to the bulk (ϵsb = 0.46 ± 0.01 eV) and the isotope specific energies, E0, sbH = 0.41 eV and E0, sbD = 0.43 eV. Detailed insights into the process of transient bulk diffusion are obtained from kinetic Monte Carlo simulations
High-yield TiO(2) nanowire synthesis and single nanowire field-effect transistor fabrication
We report a facile method for synthesizing single-crystal rutile TiO 2 nanowires using atmospheric-pressure, chemical vapor deposition with Ti and TiO as precursors. The synthesis is found to depend critically on the predeposition of a layer of metallic Ti on the Ni catalysts layer. The omission of this step seems previously to have impeded the efficient synthesis of titania nanowires. Single-nanowire field-effect transistors showed the TiO2 nanowires to be n -type semiconductors with conductance activation energy of ???58 meV.open242
Measuring transient reaction rates from nonstationary catalysts
Up to now, methods for measuring rates of reactions on catalysts required long measurement times involving signal averaging over many experiments. This imposed a requirement that the catalyst return to its original state at the end of each experiment—a complete reversibility requirement. For real catalysts, fulfilling the reversibility requirement is often impossible—catalysts under reaction conditions may change their chemical composition and structure as they become activated or while they are being poisoned through use. It is therefore desirable to develop high-speed methods where transient rates can be quickly measured while catalysts are changing. In this work, we present velocity-resolved kinetics using high-repetition-rate pulsed laser ionization and high-speed ion imaging detection. The reaction is initiated by a single molecular beam pulse incident at the surface, and the product formation rate is observed by a sequence of pulses produced by a high-repetition-rate laser. Ion imaging provides the desorbing product flux (reaction rate) as a function of reaction time for each laser pulse. We demonstrate the principle of this approach by rate measurements on two simple reactions: CO desorption from and CO oxidation on the 332 facet of Pd. This approach overcomes the time-consuming scanning of the delay between CO and laser pulses needed in past experiments and delivers a data acquisition rate that is 10–1000 times higher. We are able to record kinetic traces of CO2 formation while a CO beam titrates oxygen atoms from an O-saturated surface. This approach also allows measurements of reaction rates under diffusion-controlled conditions
NO binding energies to and diffusion barrier on Pd obtained with velocity-resolved kinetics
We report nitric oxide (NO) desorption rates from Pd(111) and Pd(332) surfaces measured with velocity-resolved kinetics. The desorption rates at the surface temperatures from 620 to 800 K span more than 3 orders of magnitude, and competing processes, like dissociation, are absent. Applying transition state theory (TST) to model experimental data leads to the NO binding energy E0 = 1.766 ± 0.024 eV and diffusion barrier DT = 0.29 ± 0.11 eV on the (111) terrace and the stabilization energy for (110)-steps ΔEST = 0.060–0.030+0.015 eV. These parameters provide valuable benchmarks for theory
Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-Atoms
A detailed velocity-resolved kinetics study of NH3 thermal desorption rates from p(2 × 2) O/Pt(111) is presented. We find a large reduction in the NH3 desorption rate due to adsorption of O-atoms on Pt(111). A physical model describing the interactions between adsorbed NH3 and O-atoms explains these observations. By fitting the model to the derived desorption rate constants, we find an NH3 stabilization on p(2 × 2) O/Pt(111) of 0.147–0.014+0.023 eV compared to Pt(111) and a rotational barrier of 0.084–0.022+0.049 eV, which is not present on Pt(111). The model also quantitatively predicts the steric hindrance of NH3 diffusion on Pt(111) due to co-adsorbed O-atoms. The derived diffusion barrier of NH3 on p(2 × 2) O/Pt(111) is 1.10–0.13+0.22 eV, which is 0.39–0.14+0.22 eV higher than that on pristine Pt(111). We find that Perdew Burke Ernzerhof (PBE) and revised Perdew Burke Ernzerhof (RPBE) exchange–correlation functionals are unable to reproduce the experimentally observed NH3–O adsorbate–adsorbate interactions and NH3 binding energies at Pt(111) and p(2 × 2) O/Pt(111), which indicates the importance of dispersion interactions for both systems
The puzzle of rapid hydrogen oxidation on Pt(111)
We have known for over 200 years that hydrogen undergoes rapid oxidation to water on Pt catalysts; yet the reaction mechanism remains unclear. Here, we report high temporal resolution measurements of the production rate of H2O from hydrogen oxidation catalysed by a Pt (111) single crystal surface with a known concentration of adsorbed oxygen atoms and a step density of approximately 0.002 ML. We obtain two rate constants describing the rise, and fall of the reaction rate between 350 and 470 K and compare our observations to modern ab initio predictions of the reaction rates in surface chemistry. Remarkably, a mechanism based on a standard set of elementary reaction steps with energies and barrier heights obtained from Density Functional Theory (DFT), predicts a rate that is four orders of magnitude smaller than observed experimentally. Furthermore, the theoretically predicted reaction rate follows first-order kinetics, whereas the experimental observations clearly show a second-order reaction. The theoretical predictions are robust – six different exchange–correlation functionals lead to similar predictions. We suggest that the reason for these disagreements is that the active sites of the catalyst and the associated elementary reactions have, so far, not been properly identified
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Chemical Dynamics at the Advanced Light Source
A day-long retreat was held January 15, 1999 to chart the future directions for chemical dynamics studies at the Advanced Light Source. This represents an important period for the Chemical Dynamics Beamline, as the hardware is well-developed, most of the initial experimental objectives have been realized and the mission is now to identify the future scientific priorities for the beamline and attract users of the highest caliber. To this end, we have developed a detailed scientific program for the near term; identified and prioritized the long range scientific opportunities, identified essential new hardware, and outlined an aggressive outreach program to involve the chemical physics community
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