Daniel R. Killelea

Bond-selective control of a heterogeneously catalyzed reaction.

Energy redistribution, including the many phonon-assisted and electronically assisted energy-exchange processes at a gas-metal interface, can hamper vibrationally mediated selectivity in chemical reactions. We establish that these limitations do not prevent bond-selective control of a heterogeneously catalyzed reaction. State-resolved gas-surface scattering measurements show that the ν1 C-H stretch vibration in trideuteromethane (CHD3) selectively activates C-H bond cleavage on a Ni(111) surface. Isotope-resolved detection reveals a CD3:CHD2 product ratio > 30:1, which contrasts with the 1:3 ratio for an isoenergetic ensemble of CHD3 whose vibrations are statistically populated. Recent studies of vibrational energy redistribution in the gas and condensed phases suggest that other gas-surface reactions with similar vibrational energy flow dynamics might also be candidates for such bond-selective control.

Chemically Accurate Simulation of a Polyatomic Molecule-Metal Surface Reaction

Although important to heterogeneous catalysis, the ability to accurately model reactions of polyatomic molecules with metal surfaces has not kept pace with developments in gas phase dynamics. Partnering the specific reaction parameter (SRP) approach to density functional theory with ab initio molecular dynamics (AIMD) extends our ability to model reactions with metals with quantitative accuracy from only the lightest reactant, H2, to essentially all molecules. This is demonstrated with AIMD calculations on CHD3 + Ni(111) in which the SRP functional is fitted to supersonic beam experiments, and validated by showing that AIMD with the resulting functional reproduces initial-state selected sticking measurements with chemical accuracy (4.2 kJ/mol ≈ 1 kcal/mol). The need for only semilocal exchange makes our scheme computationally tractable for dissociation on transition metals.

Determination of the sticking coefficient and scattering dynamics of water on ice using molecular beam techniques

The sticking coefficient for D(2)O impinging on crystalline D(2)O ice was determined for incident translational energies between 0.3 and 0.7 eV and for H(2)O on crystalline H(2)O ice at 0.3 eV. These experiments were done using directed molecular beams, allowing for precise control of the incident angle and energy. Experiments were also performed to measure the intensity and energy of the scattered molecules as a function of scattering angle. These results show that the sticking coefficient was near unity, slightly increasing with decreasing incident energy. However, even at the lowest incident energy, some D(2)O did not stick and was scattered from the ice surface. We observe under these conditions that the sticking probability asymptotically approaches but does not reach unity for water sticking on water ice. We also present evidence that the scattered fraction is consistent with a binary collision; the molecules are scattered promptly. These results are especially relevant for condensation processes occurring under nonequilibrium conditions, such as those found in astrophysical systems.

Double-Stranded Water on Stepped Platinum Surfaces

The interaction of platinum with water plays a key role in (electro)catalysis. Herein, we describe a combined theoretical and experimental study that resolves the preferred adsorption structure of water wetting the Pt(111)-step type with adjacent (111) terraces. Double stranded lines wet the step edge forming water tetragons with dissimilar hydrogen bonds within and between the lines. Our results qualitatively explain experimental observations of water desorption and impact our thinking of solvation at the Pt electrochemical interface.

Interfacial chemistry of poly(methyl methacrylate) arising from exposure to vacuum-ultraviolet light and atomic oxygen.

We herein report on the chemical and physical changes that occur in thin films of poly(methyl methacrylate), PMMA, induced by exposure to high-energy vacuum ultraviolet radiation and a supersonic beam of neutral, ground electronic state O((3)P) atomic oxygen. A combination of in situ quartz crystal microbalance and in situ Fourier-transform infrared reflection-absorption spectroscopy were used to determine the photochemical reaction kinetics and mechanisms during irradiation. The surface morphological changes were measured with atomic force microscopy. The results showed there was no enhancement in the mass loss rate during simultaneous exposure of vacuum ultraviolet (VUV) radiation and atomic oxygen. Rather, the rate of mass loss was impeded when the polymer film was exposed to both reagents. This study elucidates the kinetics of photochemical and oxidative reaction for PMMA, and shows that the synergistic effect involving VUV irradiation and exposure to ground state atomic oxygen depends substantially on the relative fluxes of these reagents.

Comparative surface dynamics of amorphous and semicrystalline polymer films

The surface dynamics of amorphous and semicrystalline polymer films have been measured using helium atom scattering. Time-of-flight data were collected to resolve the elastic and inelastic scattering components in the diffuse scattering of neutral helium atoms from the surface of a thin poly(ethylene terephthalate) film. Debye–Waller attenuation was observed for both the amorphous and semicrystalline phases of the polymer by recording the decay of elastically scattered helium atoms with increasing surface temperature. Thermal attenuation measurements in the specular scattering geometry yielded perpendicular mean-square displacements of 2.7•10-4 Å2 K-1 and 3.1•10-4 Å2 K-1 for the amorphous and semicrystalline surfaces, respectively. The semicrystalline surface was consistently ∼15% softer than the amorphous across a variety of perpendicular momentum transfers. The Debye–Waller factors were also measured at off-specular angles to characterize the parallel mean-square displacements, which were found to increase by an order of magnitude over the perpendicular mean-square displacements for both surfaces. In contrast to the perpendicular motion, the semicrystalline state was ∼25% stiffer than the amorphous phase in the surface plane. These results were uniquely accessed through low-energy neutral helium atom scattering due to the highly surface-sensitive and nonperturbative nature of these interactions. The goal of tailoring the chemical and physical properties of complex advanced materials requires an improved understanding of interfacial dynamics, information that is obtainable through atomic beam scattering methods.

Dynamics of the sputtering of water from ice films by collisions with energetic xenon atoms.

The flow of energy from the impact site of a heavy, translationally energetic xenon atom on an ice surface leads to several non-equilibrium events. The central focus of this paper is on the collision-induced desorption (sputtering) of water molecules into the gas-phase from the ice surface. Sputtering is strongly activated with respect to xenon translational energy, and a threshold for desorption was observed. To best understand these results, we discuss our findings in the context of other sputtering studies of molecular solids. The sputtering yield is quite small; differential measurements of the energy of xenon scattered from ice surfaces show that the ice efficiently accommodates the collisional energy. These results are important as they quantitatively elucidate the dynamics of such sputtering events, with implications for energetic non-equilibrium processes at interfaces.

Preparation of scanning tunneling microscopy tips using pulsed alternating current etching

An electrochemical method using pulsed alternating current etching (PACE) to produce atomically sharp scanning tunneling microscopy (STM) tips is presented. An Arduino Uno microcontroller was used to control the number and duration of the alternating current (AC) pulses, allowing for ready optimization of the procedures for both Pt:Ir and W tips using a single apparatus. W tips prepared using constant and pulsed AC power were compared. Tips fashioned using PACE were sharper than those etched with continuous AC power alone. Pt:Ir tips were prepared with an initial coarse etching stage using continuous AC power followed by fine etching using PACE. The number and potential of the finishing AC pulses was varied and scanning electron microscope imaging was used to compare the results. Finally, tip quality using the optimized procedures was verified by UHV-STM imaging. With PACE, at least 70% of the W tips and 80% of the Pt:Ir tips were of sufficiently high quality to obtain atomically resolved images of HOPG or Ni(111).

Molecular interactions with ice: Molecular embedding, adsorption, detection, and release

The interaction of atomic and molecular species with water and ice is of fundamental importance for chemistry. In a previous series of publications, we demonstrated that translational energy activates the embedding of Xe and Kr atoms in the near surface region of ice surfaces. In this paper, we show that inert molecular species may be absorbed in a similar fashion. We also revisit Xe embedding, and further probe the nature of the absorption into the selvedge. CF4 molecules with high translational energies (≥3 eV) were observed to embed in amorphous solid water. Just as with Xe, the initial adsorption rate is strongly activated by translational energy, but the CF4 embedding probability is much less than for Xe. In addition, a larger molecule, SF6, did not embed at the same translational energies that both CF4 and Xe embedded. The embedding rate for a given energy thus goes in the order Xe > CF4 > SF6. We do not have as much data for Kr, but it appears to have a rate that is between that of Xe and CF4. Tentatively, this order suggests that for Xe and CF4, which have similar van der Waals radii, the momentum is the key factor in determining whether the incident atom or molecule can penetrate deeply enough below the surface to embed. The more massive SF6 molecule also has a larger van der Waals radius, which appears to prevent it from stably embedding in the selvedge. We also determined that the maximum depth of embedding is less than the equivalent of four layers of hexagonal ice, while some of the atoms just below the ice surface can escape before ice desorption begins. These results show that energetic ballistic embedding in ice is a general phenomenon, and represents a significant new channel by which incident species can be trapped under conditions where they would otherwise not be bound stably as surface adsorbates. These findings have implications for many fields including environmental science, trace gas collection and release, and the chemical composition of astrophysical icy bodies in space.

Exposure of Pt(5 5 3) and Rh(1 1 1) to atomic and molecular oxygen: do defects enhance subsurface oxygen formation?

Subsurface oxygen is known to form in transition metals, and is thought to be an important aspect of their ability to catalyze chemical reactions. The formation of subsurface oxygen is not, however, equivalent across all catalytically relevant metals. As a result, it is difficult to predict the stability and ease of the formation of subsurface oxygen in metals, as well as how the absorbed oxygen affects the chemical and physical properties of the metal. In comparing how a stepped platinum surface, Pt(5 5 3), responds to exposure to gas-phase oxygen atoms under ultra-high vacuum conditions to planar Rh(1 1 1), we are able to determine what role, if any, steps have on the capacity of a metal for subsurface oxygen formation. Despite the presence of regular defects, we found that only surface-bound oxygen formed on Pt(5 5 3). Alternatively, on the Rh(1 1 1) surface, oxygen readily absorbed into the selvedge of the metal. These results suggest that defects alone are insufficient for the formation of subsurface oxygen, and the ability of the metal to absorb oxygen is the primary factor in the formation and stabilization of subsurface oxygen.