Chemical dynamics from the gas-phase to surfaces

The field of gas-phase chemical dynamics has developed superb experimental methods to probe the detailed outcome of gas-phase chemical reactions. These experiments inspired and benchmarked first principles dynamics simulations giving access to an atomic scale picture of the motions that underlie these reactions. This fruitful interplay of experiment and theory is the essence of a dynamical approach perfected on gas-phase reactions, the culmination of which is a standard model of chemical reactivity involving classical trajectories or quantum wave packets moving on a Born–Oppenheimer potential energy surface. Extending the dynamical approach to chemical reactions at surfaces presents challenges of complexity not found in gas-phase study as reactive processes often involve multiple steps, such as inelastic molecule-surface scattering and dissipation, leading to adsorption and subsequent thermal desorption and or bond breaking and making. This paper reviews progress toward understanding the elementary processes involved in surface chemistry using the dynamical approach

Spin-forbidden carbon–carbon bond formation in vibrationally excited α-CO

Fourier transform infrared spectroscopy of laser-irradiated cryogenic crystals shows that vibrational excitation of CO leads to the production of equal amounts of CO2 and C3O2. The reaction mechanism is explored using electronic structure calculations, demonstrating that the lowest-energy pathway involves a spin-forbidden reaction of (CO)2 yielding C(3P) + CO2. C(3P) then undergoes barrierless recombination with two other CO molecules forming C3O2. Calculated intersystem crossing rates support the spin-forbidden mechanism, showing subpicosecond spin-flipping time scales for a (CO)2 geometry that is energetically consistent with states accessed through vibrational energy pooling. This spin-flip occurs with an estimated ∼4% efficiency; on the singlet surface, (CO)2 reconverts back to CO monomers, releasing heat which induces CO desorption. The discovery that vibrational excitation of condensed-phase CO leads to spin-forbidden C−C bond formation may be important to the development of accurate models of interstellar chemistry

Condensed-phase isomerization through tunnelling gateways

Quantum mechanical tunnelling describes transmission of matter waves through a barrier with height larger than the energy of the wave. Tunnelling becomes important when the de Broglie wavelength of the particle exceeds the barrier thickness; because wavelength increases with decreasing mass, lighter particles tunnel more efficiently than heavier ones. However, there exist examples in condensed-phase chemistry where increasing mass leads to increased tunnelling rates. In contrast to the textbook approach, which considers transitions between continuum states, condensed-phase reactions involve transitions between bound states of reactants and products. Here this conceptual distinction is highlighted by experimental measurements of isotopologue-specific tunnelling rates for CO rotational isomerization at an NaCl surface, showing nonmonotonic mass dependence. A quantum rate theory of isomerization is developed wherein transitions between sub-barrier reactant and product states occur through interaction with the environment. Tunnelling is fastest for specific pairs of states (gateways), the quantum mechanical details of which lead to enhanced cross-barrier coupling; the energies of these gateways arise nonsystematically, giving an erratic mass dependence. Gateways also accelerate ground-state isomerization, acting as leaky holes through the reaction barrier. This simple model provides a way to account for tunnelling in condensed-phase chemistry, and indicates that heavy-atom tunnelling may be more important than typically assumed

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

Generation of Tunable Narrow Bandwidth Nanosecond Pulses in the Deep Ultraviolet for Efficient Optical Pumping and High Resolution Spectroscopy

Nanosecond optical pulses with high power and spectral brightness in the deep ultraviolet (UV) region have been produced by sum frequency mixing of nearly transform-limited-bandwidth IR light originating from a home-built injection-seeded ring cavityoptical parametric oscillator(OPO) and the fourth harmonic beam of an injection-seeded Nd:YAG laser used simultaneously to pump the OPO with the second harmonic. We demonstrate UV output, tunable from 204 to 207 nm, which exhibits pulse energies up to 5 mJ with a bandwidth better than [Math Processing Error]. We describe how the approach shown in this paper can be extended to wavelengths shorter than 185 nm. The injection-seeded OPO provides high conversion efficiency ([Math Processing Error] overall energy conversion) and superior beam quality required for highly efficient downstream mixing where sum frequencies are generated in the UV. The frequency stability of the system is excellent, making it highly suitable for optical pumping. We demonstrate high resolution spectroscopy as well as optical pumping using laser-induced fluorescence and stimulated emission pumping, respectively, in supersonic pulsed molecular beams of nitric oxide

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

Generation of Tunable Narrow Bandwidth Nanosecond Pulses in the Deep Ultraviolet for Efficient Optical Pumping and High Resolution Spectroscopy

Nanosecond optical pulses with high power and spectral brightness in the deep ultraviolet (UV) region have been produced by sum frequency mixing of nearly transform-limited-bandwidth IR light originating from a home-built injection-seeded ring cavityoptical parametric oscillator(OPO) and the fourth harmonic beam of an injection-seeded Nd:YAG laser used simultaneously to pump the OPO with the second harmonic. We demonstrate UV output, tunable from 204 to 207 nm, which exhibits pulse energies up to 5 mJ with a bandwidth better than [Math Processing Error]. We describe how the approach shown in this paper can be extended to wavelengths shorter than 185 nm. The injection-seeded OPO provides high conversion efficiency ([Math Processing Error] overall energy conversion) and superior beam quality required for highly efficient downstream mixing where sum frequencies are generated in the UV. The frequency stability of the system is excellent, making it highly suitable for optical pumping. We demonstrate high resolution spectroscopy as well as optical pumping using laser-induced fluorescence and stimulated emission pumping, respectively, in supersonic pulsed molecular beams of nitric oxide