Alan C. Luntz

Communications: Elementary oxygen electrode reactions in the aprotic Li-air battery

We discuss the electrochemical reactions at the oxygen electrode of an aprotic Li-air battery. Using density functional theory to estimate the free energy of intermediates during the discharge and charge of the battery, we introduce a reaction free energy diagram and identify possible origins of the overpotential for both processes. We also address the question of electron conductivity through the Li(2)O(2) electrode and show that in the presence of Li vacancies Li(2)O(2) becomes a conductor.

How adiabatic is activated adsorption/associative desorption?

Using density-functional theory we calculate friction coefficients describing the damping of nuclear motion into electron-hole pair excitation for the two best-known examples of activated adsorption: H2 dissociation on a Cu(111) surface and N2 dissociation on a Ru(0001) surface. In both cases, the frictions increase dramatically along the reaction path towards the transition state and can be an order of magnitude larger there than typical in the molecularly adsorbed state. In addition, the frictions for N2/Ru(0001) are typically an order of magnitude larger than for H2/Cu(111). We rationalize these trends in terms of the electron structure as the systems proceed to dissociation along the reaction paths. Combining these friction coefficients with the potential-energy surface in quasiclassical dynamics allows first-principles studies of the importance of the breakdown in the Born-Oppenheimer approximation in describing the chemistry. We find that nonadiabatic effects are minimal for the H2/Cu(111) system, but are quite important for N2/Ru(0001).

Influence of surface morphology on D2 desorption kinetics from amorphous solid water

The influence of surface morphology/porosity on the desorption kinetics of weakly bound species was investigated by depositing D2 on amorphous solid water (ASW) films grown by low temperature vapor deposition under various conditions and with differing thermal histories. A broad distribution of binding energies of the D2 monolayer on nonporous and porous ASW was measured experimentally and correlated by theoretical calculations to differences in the degree of coordination of the adsorbed H2 (D2) to H2O molecules in the ASW depending on the nature of the adsorption site, i.e., surface valleys vs surface peaks in a nanoscale rough film surface. For porous films, the effect of porosity on the desorption kinetics was observed to be a reduction in the desorption rate with film thickness and a change in peak shape. This can be partly explained by fast diffusion into the ASW pore structure via a simple one-dimensional diffusion model and by a change in binding energy statistics with increasing total effective surface area. Furthermore, the D2 desorption kinetics on thermally annealed ASW films were investigated. The main effect was seen to be a reduction in porosity and in the number of highly coordinated binding sites with anneal temperature due to ASW restructuring and pore collapse. These results contribute to the understanding of desorption from porous materials and to the development of correct models for desorption from and catalytic processes on dust grain surfaces in the interstellar medium.

Indirect evidence for strong nonadiabatic coupling in N2 associative desorption from and dissociative adsorption on Ru(0001)

This paper reports the simultaneous internal state and translational energy resolved associative desorption flux of N2 from Ru(0001) using two different experimental approaches. Both experiments show that the nascent N2 is formed with little vibrational excitation and that the total excitation in all N2 degrees of freedom accounts for only 13 of the barrier energy. Roughly 23 of the energy necessary to surmount the barrier is lost to the surface in desorption. This behavior, as well as the unusual behavior noted previously in direct measurements of dissociative adsorption, both imply strong vibrational quenching in reactive trajectories passing over the high exit channel (vibrational) barrier. Adiabatic quasiclassical dynamical calculations based on the ab initio potential energy surface and various models of coupling to the lattice are not qualitatively consistent with N2 vibrational damping to phonons. However, including a strong nonadiabatic coupling of the vibrational coordinate to electron–hole pairs...

Theoretical evidence for nonadiabatic vibrational deexcitation in H2(D2) state-to-state scattering from Cu(100)

Dynamical calculations are presented for electronically nonadiabatic vibrational deexcitation of H2 and D2 in scattering from Cu(111). Both the potential energy surface and the nonadiabatic coupling strength were obtained from density functional calculations. The theoretically predicted magnitude of the deexcitation and its dependence on incident energy and isotope are all in agreement with state-to-state scattering experiments [on Cu(100)], and this gives indirect evidence for a nonadiabatic mechanism of the observed deexcitation. Direct evidence could be obtained by measuring the chemicurrent associated with the deexcitation, and its properties have been predicted.

High translational energy release in H2 (D2) associative desorption from H (D) chemisorbed on C(0001)

Highly energetic translational energy distributions are reported for hydrogen and deuterium molecules desorbing associatively from the atomic chemisorption states on highly oriented pyrolytic graphite (HOPG). Laser assisted associative desorption is used to measure the time of flight of molecules desorbing from a hydrogen (deuterium) saturated HOPG surface produced by atomic exposure from a thermal atom source at around 2100 K. The translational energy distributions normal to the surface are very broad, from approximately 0.5 to approximately 3 eV, with a peak at approximately 1.3 eV. The highest translational energy measured is close to the theoretically predicted barrier height. The angular distribution of the desorbing molecules is sharply peaked along the surface normal and is consistent with thermal broadening contributing to energy release parallel to the surface. All results are in qualitative agreement with recent density functional theory calculations suggesting a lowest energy para-type dimer recombination path.

N2 dissociative adsorption on Ru(0001): The role of energy loss

New molecular beam experiments on the dissociation probability S0 for N2 on Ru(0001) are presented. These are in general agreement with prior measurements and exhibit very unusual behavior; a very slow increase of S0 with incident kinetic energy E and the fact that S0 is still only ∼10−3 at incident energies considerably above the barrier. A simple dynamical model is developed to describe this unusual sticking behavior. The key aspect is that there is considerable energy loss Δ from E upon initial impact with the surface (principally to the lattice) and only E−Δ is then available to surmount the activation barrier in the exit channel. Using experimentally measured values of Δ from scattering experiments gives good qualitative agreement of this model with the measured S0. One implication of the strong energy loss is that there is an apparent violation of detailed balance when comparing only the reactive fluxes of activated adsorption and associative desorption.

CH4 dissociation on Ru(0001): A view from both sides of the barrier

This paper reports measurements of both dissociative adsorption on and associative desorption from CH4 on Ru(0001). We consider the former a view of dissociation from the front side of the barrier, while the latter is considered as a view of dissociation from the back side of the barrier. A combination of both previous and new molecular beam measurements of dissociative adsorption shows that S0 depends on all experimental variables (E, Tn, Ts and isotope) in a manner similar to other close-packed transition metals. The interpretation of this behavior in terms of a theoretical description of the dissociation is discussed critically, with special emphasis on insights from new theoretical studies. The energy-resolved desorption flux Df(E,Ts) is obtained in associative desorption experiments using the technique of laser assisted associative desorption (LAAD). Measurements at several Ts allow both a direct determination of the adiabatic barrier V*(0) and considerable insight into the dynamics of dissociation. ...

Dynamics of ammonia decomposition on Ru(0001)

Using supersonic molecular beam techniques we have investigated the dissociative adsorption of NH3 on a Ru(0001) surface. At high incident energies, the dissociation increases substantially due to a direct breaking of the N–H bond on impact with the surface. For low incident translational energies, the dissociation depends on surface temperature Ts in an unusual manner, peaking sharply around 400 K. Increasing the surface defect density by low-fluence Ar+ sputtering strongly enhances the dissociation probability while preserving the overall Ts-dependence. We interpret the low incident energy behavior as due to a mechanism in which a molecular precursor must undergo diffusion to defects before dissociating. At the lowest surface temperatures, dissociation is limited by the diffusion of the reaction products away from the defects in order to reactivate them. A kinetic model based on this mechanism is developed which is in good agreement with all experimental observations.

State resolved inelastic scattering of N2 from Ru(0001)

Detailed measurements of state resolved inelastic scattering of N2 from Ru(0001) are reported for a wide range of initial energies (0–3 eV) and angles of incidence. The ion time-of-flight resonantly enhanced multiphoton ionization (REMPI) detection scheme developed here and used with cw molecular beams simultaneously measures the internal quantum state and translational energy normal to the sample surface. Doppler broadening of the REMPI spectrum of scattered particles yields the dispersion in scattering out of plane. The results are qualitatively similar to inelastic N2 scattering studies for a wide variety of other metal surfaces; i.e., no observable vibrational excitation, weak rotational excitation described as a Boltzmann distribution, strong surface excitation depending upon the incident normal energy, and an anticorrelation between rotational and surface excitation. The absence of any vibrational excitation at E≈3 eV is inconsistent with adiabatic model dynamics based on the ab initio potential-ene...