Insights into Reaction Kinetics in Confined Space: Real Time Observation of Water Formation under a Silica Cover.

We offer a comprehensive approach to determine how physical confinement can affect the water formation reaction. By using free-standing crystalline SiO2 bilayer supported on Ru(0001) as a model system, we studied the water formation reaction under confinement in situ and in real time. Low-energy electron microscopy reveals that the reaction proceeds via the formation of reaction fronts propagating across the Ru(0001) surface. The Arrhenius analyses of the front velocity yield apparent activation energies (Eaapp) of 0.32 eV for the confined and 0.59 eV for the nonconfined reaction. DFT simulations indicate that the rate-determining step remains unchanged upon confinement, therefore ruling out the widely accepted transition state effect. Additionally, H2O accumulation cannot explain the change in Eaapp for the confined cases studied because its concentration remains low. Instead, numerical simulations of the proposed kinetic model suggest that the H2 adsorption process plays a decisive role in reproducing the Arrhenius plots.

A Silica Bilayer Supported on Ru(0001): Following the Crystalline-to Vitreous Transformation in Real Time with Spectro-microscopy.

The crystalline-to-vitreous phase transformation of a SiO2 bilayer supported on Ru(0001) was studied by time-dependent LEED, local XPS, and DFT calculations. The silica bilayer system has parallels to 3D silica glass and can be used to understand the mechanism of the disorder transition. DFT simulations show that the formation of a Stone-Wales-type of defect follows a complex mechanism, where the two layers show decoupled behavior in terms of chemical bond rearrangements. The calculated activation energy of the rate-determining step for the formation of a Stone-Wales-type of defect (4.3 eV) agrees with the experimental value. Charge transfer between SiO2 bilayer and Ru(0001) support lowers the activation energy for breaking the Si-O bond compared to the unsupported film. Pre-exponential factors obtained in UHV and in O2 atmospheres differ significantly, suggesting that the interfacial ORu underneath the SiO2 bilayer plays a role on how the disordering propagates within the film.

Attosecond Dynamics of sp-Band Photoexcitation.

We report measurements of the temporal dynamics of the valence band photoemission from the magnesium (0001) surface across the resonance of the Γ[over ¯] surface state at 134 eV and link them to observations of high-resolution synchrotron photoemission and numerical calculations of the time-dependent Schrödinger equation using an effective single-electron model potential. We observe a decrease in the time delay between photoemission from delocalized valence states and the localized core orbitals on resonance. Our approach to rigorously link excitation energy-resolved conventional steady-state photoemission with attosecond streaking spectroscopy reveals the connection between energy-space properties of bound electronic states and the temporal dynamics of the fundamental electronic excitations underlying the photoelectric effect.

Water Formation under Silica Thin Films: Real-Time Observation of a Chemical Reaction in a Physically Confined Space.

Using low-energy electron microscopy and local photoelectron spectroscopy, water formation from adsorbed O and H2 on a Ru(0001) surface covered with a vitreous SiO2 bilayer (BL) was investigated and compared to the same reaction on bare Ru(0001). In both cases the reaction is characterized by moving reaction fronts. The reason for this might be related to the requirement of site release by O adatoms for further H2 -dissociative adsorption. Apparent activation energies (Eaapp ) are found for the front motion of 0.59 eV without cover and 0.27 eV under cover. We suggest that the smaller activation energy but higher reaction temperature for the reaction on the SiO2 BL covered Ru(0001) surface is due to a change of the rate-determining step. Other possible effects of the cover are discussed. Our results give the first values for Eaapp in confined space.

A Two-Dimensional 'Zigzag' Silica Polymorph on a Metal Support.

We present a new polymorph of the two-dimensional (2D) silica film with a characteristic 'zigzag' line structure and a rectangular unit cell which forms on a Ru(0001) metal substrate. This new silica polymorph may allow for important insights into growth modes and transformations of 2D silica films as a model system for the study of glass transitions. Based on scanning tunneling microscopy, low energy electron diffraction, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy measurements on the one hand, and density functional theory calculations on the other, a structural model for the 'zigzag' polymorph is proposed. In comparison to established monolayer and bilayer silica, this 'zigzag' structure system has intermediate characteristics in terms of coupling to the substrate and stoichiometry. The silica 'zigzag' phase is transformed upon reoxidation at higher annealing temperature into a SiO2 silica bilayer film which is chemically decoupled from the substrate.

Self-Assembly of Graphene Nanoblisters Sealed to a Bare Metal Surface.

The possibility to intercalate noble gas atoms below epitaxial graphene monolayers coupled with the instability at high temperature of graphene on the surface of certain metals has been exploited to produce Ar-filled graphene nanosized blisters evenly distributed on the bare Ni(111) surface. We have followed in real time the self-assembling of the nanoblisters during the thermal annealing of the Gr/Ni(111) interface loaded with Ar and characterized their morphology and structure at the atomic scale. The nanoblisters contain Ar aggregates compressed at high pressure arranged below the graphene monolayer skin that is decoupled from the Ni substrate and sealed only at the periphery through stable C-Ni bonds. Their in-plane truncated triangular shapes are driven by the crystallographic directions of the Ni surface. The nonuniform strain revealed along the blister profile is explained by the inhomogeneous expansion of the flexible graphene lattice that adjusts to envelop the Ar atom stacks.

Ultrafast charge transfer at monolayer graphene surfaces with varied substrate coupling.

The charge transfer rates of a localized excited electron to graphene monolayers with variable substrate coupling have been investigated by the core hole clock method with adsorbed argon. Expressed as charge transfer times, we find strong variations between ~3 fs (on graphene "valleys" on Ru(0001)) to ~16 fs (quasi-free graphene on SiC, O/Ru(0001), or SiO2/Ru). The values for the "hills" on Gr/Ru and on Gr/Pt(111) are in between, with the ratio 1.7 between the charge transfer times measured on "hills" and "valleys" of Gr/Ru. We discuss the results for Gr on metals in terms of hybridized Ru-C orbitals, which change with the relative Gr-Ru alignment and distance. The charge transfer on the decoupled graphene layers must represent the intrinsic coupling to the graphene empty π* states. Its low rate may be influenced by processes retarding the spreading of charge after transfer.

Electronically induced surface reactions: evolution, concepts, and perspectives.

This is a personal account of the development of the title subject which is the broader field encompassing surface photochemistry. It describes the early times when the main interest centered on desorption induced by slow electrons, follows its evolution in experiment (use of synchrotron radiation and connections to electron spectroscopies; use of lasers) and mechanisms, and briefly mentions the many different subfields that have evolved. It discusses some practically important aspects and applications and ends with an account of an evolving new subfield, the application to photochemistry on nanoparticles.

Enhanced photoinduced desorption from metal nanoparticles by photoexcitation of confined hot electrons using femtosecond laser pulses.

Strong fluence dependence of photodesorption cross sections is observed in femtosecond laser photodesorption of NO from (NO)2 on silver nanoparticles, in contrast to femtosecond photodesorption on bulk metals. The time scale of excitation buildup is found to be equal or less than the pulse duration of ∼100 fs; NO translational energies are independent of fluence and pulse duration. We propose a nanoparticle-specific nonlinear mechanism in which, due to confinement, strongly nonthermal hot-electron distributions are maintained during the femtosecond pulses, enhancing the normal desorption pathway.

State-resolved investigation of the photodesorption dynamics of NO from (NO)2 on Ag nanoparticles of various sizes in comparison with Ag(111).

The translational and internal state energy distributions of NO desorbed by laser light (2.3, 3.5, and 4.7 eV) from adsorbed (NO)(2) on Ag nanoparticles (NPs) (mean diameters, D = 4, 8, and 11 nm) have been investigated by the (1 + 1) resonance enhanced multiphoton ionization technique. For comparison, the same experiments have also been carried out on Ag(111). Detected NO molecules are hyperthermally fast and both rotationally and vibrationally hot, with temperatures well above the sample temperature. The translational and rotational excitations are positively correlated, while the vibrational excitation is decoupled from the other two degrees of freedom. Most of the energy content of the desorbing NO is contained in its translation. The translational and internal energy distributions of NO molecules photodesorbed by 2.3, 3.5, and in part also 4.7 eV light are approximately constant as a function of Ag NPs sizes, and they are the same on Ag(111). This suggests that for these excitations a common mechanism is operative on the bulk single crystal and on NPs, independent of the size regime. Notably, despite the strongly enhanced cross section seen on NP at 3.5 eV excitation energy in p-polarization, i.e., in resonance with the plasmon excitation, the mechanism is also unchanged. At 4.7 eV and for small particles, however, an additional desorption channel is observed which results in desorbates with higher energies in all degrees of freedom. The results are well compatible with our earlier measurements of size-dependent translational energy distributions. We suggest that the broadly constant mechanism over most of the investigated range runs via a transient negative ion state, while at high excitation energy and for small particles the transient state is suggested to be a positive ion.

UV photo-dissociation and photodesorption of N2O on Ag(111).

Nanosecond laser induced photoreactions of N2O adsorbed on Ag(111) have been studied by temperature programmed desorption (TPD) and mass-selected, angle-dependent time-of-flight (MS-TOF) measurements of neutral desorbing particles. N2O molecules in the first monolayer are thermally inert but photo-dissociate into N2 + O, or photodesorb molecularly or dissociatively, at photon energies above 3.5 eV. We have found that TOF spectra of photodesorbed N2 as well as of N2O measured at hν = 4.7 eV consist of two velocity components. The desorption flux of the fastest component of N2O peaks ∼ 25° off the surface normal, whereas the others are directed in the surface normal. Origins and photo-excitation as well as photodesorption mechanisms of the N2O and N2 signals are discussed.

Photoinduced abstraction reactions within NO dimers on Ag(111).

Nanosecond laser-induced photoreactions of (NO)(2) adsorbed on Ag(111) at 75 K are investigated by mass-selected photoinduced desorption (PID) and time-of-flight (TOF) measurements. It has been found that N(2) as well as N(2)O is formed by a photoinduced abstraction reaction within a single (NO)(2). The photoproduct N(2) desorbs with a very high translational temperature (5700 K) as a result of strong repulsion by the surface upon its formation. The Ag surface shortens the N-N bond of (NO)(2) to enable N(2)O and N(2) formation.

Size effects in thermal and photochemistry of (NO)2 on Ag nanoparticles.

NO dimers adsorbed on alumina supported silver nanoparticles (Ag NPs, radii R approximately 1-6 nm) show decreasing desorption temperatures and complex behavior of photoinduced desorption with decreasing NP size. In particular, for resonant excitation of the (1,0) Mie plasmon at 3.5 eV the photoinduced desorption cross section increases with 1/R, showing a pronounced enhancement (40 times) at R approximately 2.5 nm compared to Ag(111). At 4.7 eV the translational temperature of photodesorbed NO increases strongly with 1/R. We discuss these trends and peculiarities in terms of the size-dependent properties of the Ag NPs.

Ultrafast charge transfer at surfaces accessed by core electron spectroscopies.

Charge transfer at surfaces, which is very important for surface photochemistry and other processes, can be extremely fast. This tutorial review shows how high resolution correlated excitation/decay spectroscopies of core excitations can be used to obtain charge transfer times at surfaces around or below 1 fs. Some results are described in more detail, and their meaning and theoretical modelling are discussed. A brief comparison to laser methods shows that there are differences in the processes they look at.

Hyperthermal chaotic photodesorption of xenon from alumina-supported silver nanoparticles: plasmonic coupling and plasmon-induced desorption.

Excitation of Xe monolayers on alumina-supported silver nanoparticles (AgNPs) by laser light in the (1,0) Mie plasmon resonance can lead to desorption of Xe atoms with hyperthermal energy and chaotic time structure. The chaotic behavior is most likely due to plasmonic coupling between AgNPs. We argue that the desorption is induced by direct energy transfer to the adsorbate from the Pauli repulsion of the collectively oscillating electrons of the plasmon at the surface. A simple model calculation shows that this is possible. A connection between both effects appears likely.