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Molecular beam experiments in which gas molecules are scattered from liquids provide detailed, microscopic perspectives on the gas–liquid interface. Extending these methods to volatile liquids while maintaining the ability to measure product energy and angular distributions presents a significant challenge. The incorporation of flat liquid jets into molecular beam scattering experiments in our laboratory has allowed us to demonstrate their utility in uncovering dynamics in this complex chemical environment. Here, we summarize recent work on the evaporation and scattering of Ne, CD4, ND3, and D2O from a dodecane flat liquid jet and present first results on the evaporation and scattering of Ar from a cold salty water jet. In the evaporation experiments, Maxwell–Boltzmann flux distributions with a cosθ angular distribution are observed. Scattering experiments reveal both impulsive scattering (IS) and trapping followed by thermal desorption (TD). Super-specular scattering is observed for all four species scattered from dodecane and is attributed to anisotropic momentum transfer to the liquid surface. In the IS channel, rotational excitation of the polyatomic scatterers is a significant energy sink, and these species accommodate more readily on the dodecane surface compared to Ne. Our preliminary results on cold salty water jets suggest that Ar atoms undergo some vapor-phase collisions when evaporating from the liquid surface. Initial scattering experiments characterize the mechanisms of Ar interacting with an aqueous jet, allowing for comparison to dodecane systems. Key Points: Molecular beam scattering from flat liquid jets is a powerful technique to elucidate mechanistic detail at the gas–liquid interface. Previous dodecane scattering experiments have uncovered angularly-resolved thermal desorption fractions and energy transfer at the interface for several small molecule scatterers. Preliminary results on scattering from cold salty water reveal mechanisms of interaction between argon and an aqueous jet.

This work presents systematic comparisons between classical molecular dynamics (cMD) and quantum dynamics (QD) simulations of 15-dimensional and 75-dimensional models in their description of H atom scattering from graphene. We use an experimentally validated full-dimensional neural network potential energy surface of a hydrogen atom interacting with a large cell of graphene containing 24 carbon atoms. For quantum dynamics simulations, we apply Monte Carlo canonical polyadic decomposition to transform the original potential energy surface (PES) into a sum of products form and use the multi-layer multi-configuration time-dependent Hartree method to simulate the quantum scattering of a hydrogen or deuterium atom with an initial kinetic energy of 1.96 or 0.96 eV and an incident angle of 0°, i.e., perpendicular to the graphene surface. The cMD and QD initial conditions have been carefully chosen in order to be as close as possible. Our results show little differences between cMD and QD simulations when the incident energy of the H atom is equal to 1.96 eV. However, a large difference in sticking probability is observed when the incident energy of the H atom is equal to 0.96 eV, indicating the predominance of quantum effects. To the best of our knowledge, our work provides the first benchmark of quantum against classical simulations for a system of this size with a realistic PES. Additionally, new projectors are implemented in the Heidelberg multi-configuration time-dependent Hartree package for the calculation of the atom scattering energy transfer distribution as a function of outgoing angles. [ABSTRACT FROM AUTHOR]

The Born–Oppenheimer approximation (BOA), which serves as the basis for our understanding of chemical bonding, reactivity and dynamics, is routinely violated for vibrationally inelastic scattering of molecules at metal surfaces. The title-field therefore represents a fascinating challenge to our conventional wisdom calling for new concepts that involve explicit electron dynamics occurring in concert with nuclear motion. Here, we review progress made in this field over the last decade, which has witnessed dramatic advances in experimental methods, thereby providing a much more extensive set of diverse observations than has ever before been available. We first review the experimental methods used in this field and then provide a systematic tour of the vast array of observations that are currently available. We show how these observations – taken together and without reference to computational simulations – lead us to a simple and intuitive picture of BOA failure in molecular dynamics at metal surfaces, one where electron transfer between the molecule and the metal plays a preeminent role. We also review recent progress made in the theory of electron transfer mediated BOA failure in molecule–surface interactions, describing the most important methods and their ability to reproduce experimental observation. Finally, we outline future directions for research and important unanswered questions. [ABSTRACT FROM AUTHOR]

Visible-light absorption and transport of the resultant electronic excitations to a reaction centre through Förster resonance energy transfer.sup.1-3 (FRET) are critical to the operation of biological light-harvesting systems.sup.4, and are used in various artificial systems made of synthetic dyes.sup.5, polymers.sup.6 or nanodots.sup.7,8. The fundamental equations describing FRET are similar to those describing vibration-to-vibration (V-V) energy transfer.sup.9, and suggest that transport and localization of vibrational energy should, in principle, also be possible. Although it is known that vibrational excitation can promote reactions.sup.10-16, transporting and concentrating vibrational energy has not yet been reported. We have recently demonstrated orientational isomerization enabled by vibrational energy pooling in a CO adsorbate layer on a NaCl(100) surface.sup.17. Here we build on that work to show that the isomerization reaction proceeds more efficiently with a thick .sup.12C.sup.16O overlayer that absorbs more mid-infrared photons and transports the resultant vibrational excitations by V-V energy transfer to a .sup.13C.sup.18O-NaCl interface. The vibrational energy density achieved at the interface is 30 times higher than that obtained with direct excitation of the interfacial CO. We anticipate that with careful system design, these concepts could be used to drive other chemical transformations, providing new approaches to condensed phase chemistry. Infrared absorption by a thick CO crystal produces many vibrational quanta that can be transported and concentrated at a salt interface to drive orientational isomerization of CO molecules with enhanced efficiency., Author(s): Jascha A. Lau [sup.1] [sup.2] , Li Chen [sup.2] [sup.5] , Arnab Choudhury [sup.1] [sup.2] , Dirk Schwarzer [sup.2] , Varun B. Verma [sup.3] , Alec M. Wodtke [sup.1] [...]

This document is an erratum for an article titled "Quantum and classical molecular dynamics for H atom scattering from graphene" published in the Journal of Chemical Physics. The erratum states that Figure 12 in the original article was mixed with other results and provides the correct figure, which is now labeled as Figure 1. The figure shows the outgoing kinetic energy distribution for H atoms with different initial kinetic energies attacking different parts of the graphene structure. The authors of the original article are Lei Shi, Markus Schröder, Hans-Dieter Meyer, Daniel Peláez, Alec M. Wodtke, Kai Golibrzuch, Anna-Maria Schönemann, Alexander Kandratsenka, and Fabien Gatti. [Extracted from the article]

Uncovering the role of reaction intermediates is crucial to developing an understanding of heterogeneous catalysis because catalytic reactions often involve complex networks of elementary steps. Identifying the reaction intermediates is often difficult because their short lifetimes and low concentrations make it difficult to observe them with surface sensitive spectroscopic techniques. In this paper we report a different approach to identify intermediates for the formic acid decomposition reaction on Pd(111) and Pd(332) based on accurate measurements of isotopologue specific thermal reaction rates. At low surface temperatures (∼400 K) CO2 formation is the major reaction pathway. The CO2 kinetic data show this occurs via two temporally resolved reaction processes. Thus, there must be two parallel pathways which we attribute to the participation of two intermediate species in the reaction. Isotopic substitution reveals large and isotopologue specific kinetic isotope effects that allow us to identify the two key intermediates as bidentate formate and carboxyl. The decomposition of the bidentate formate is substantially slower than that of carboxyl. On Pd(332), at high surface temperatures (643 K to 693 K) we observe both CO and CO2 production. The observation of CO formation reinforces the conclusion of calculations that suggest the carboxyl intermediate plays a major role in the water–gas shift reaction, where carboxyl exhibits temperature dependent branching between CO2 and CO. [ABSTRACT FROM AUTHOR]

Previously reported TiO2 nanowire fabrication from Ni catalysts shows a surprising amount of phosphorous (P) contamination incorporated into the seed particle. We proposed this unintentional P-doping of Ni particles aids the mechanism for nanowire growth and occurs by an alternative pathway from the Vapor-Liquid-Solid (VLS) mechanism. To confirm this new mechanism, mixed phase NiP/Ni2P (NixPy) and Ni2P nanoparticles were fabricated and the central role of phosphorous in TiO 2 nanowire synthesis confirmed. This newly developed P-assisted fabrication method yielded crystalline rutile TiO2 nanowires. In this mechanism solid, quasi-spherical catalyst particles attached to the ends of nanowires and surrounded by a Ni/P liquid shell are responsible for the nanowire growth. The growing end of the nanowire appears to form a "tangent- plane" to the solid catalyst core with the liquid shell wetting and occupying the interstice between the catalyst and the nanowire. In Ni xPy assisted growth, nanowire diameters occurred as small as 12.3 nm, some of the thinnest yet reported TiO2 nanowires resulting from atmospheric-pressure chemical vapor deposition (APCVD) growth. © The Royal Society of Chemistry 2013.

Energy transferred in atom‐surface collisions typically depends strongly on projectile mass, an effect that can be experimentally detected by isotopic substitution. In this work, we present measurements of inelastic H and D atom scattering from a semiconducting Ge(111)c(2×8) surface exhibiting two scattering channels. The first channel shows the expected isotope effect and is quantitatively reproduced by electronically adiabatic molecular dynamics simulations. The second channel involves electronic excitations of the solid and, surprisingly, exhibits almost no isotope effect. We attribute these observations to scattering dynamics, wherein the likelihood of electronic excitation varies with the impact site engaged in the interaction. Key Points: Previous work revealed that H atoms with sufficient translational energy can excite electrons over the band gap of a semiconductor in a surface collision.We studied the isotope effect of the energy transfer by H/D substitution and performed band structure calculations to elucidate the underlying excitation mechanism.Our results suggest a site‐specific mechanism that requires the atom to hit a specific surface site to excite an electron‐hole pair. [ABSTRACT FROM AUTHOR]

We report inelastic differential scattering experiments for energetic H and D atoms colliding at a Pt(111) surface with and without adsorbed O atoms. Dramatically, more energy loss is seen for scattering from the Pt(111) surface compared to p(2 × 2) O on Pt(111), indicating that O adsorption reduces the probability of electron–hole pair (EHP) excitation. We produced a new full-dimensional potential energy surface for H interaction with O/Pt that reproduces density functional theory energies accurately. We then attempted to model the EHP excitation in H/D scattering with molecular dynamics simulations employing the electronic density information from the Pt(111) to calculate electronic friction at the level of the local density friction approximation (LDFA). This approach, which assumes that O atoms simply block the Pt atom from the approaching H atom, fails to reproduce experiment due to the fact that the effective collision cross section of the O atom is only 10% of the area of the surface unit cell. An empirical adiabatic sphere model that reduces electronic nonadiabaticity within an O–Pt bonding length scale of 2.8 Å reproduces experiment well, suggesting that the electronic structure changes induced by chemisorption of O atoms nearly remove the H atom's ability to excite EHPs in the Pt. Alternatives to LDFA friction are needed to account for this adsorbate effect. [ABSTRACT FROM AUTHOR]

Using molecular beam cooled samples and quantum state-selective detection, we observe v = 0 → 1 vibrational transitions when HCl (v = 0) collides with an Ag(111) surface and derive both the incidence energy and surface temperature dependence of the transition probability. Our observations reveal that both electronically adiabatic and non-adiabatic mechanisms are at play in this inelastic process. A comparison to other systems shows similarities and trends that are consistent with an electron transfer mechanism forming a transient HCl−. For example, the electronically nonadiabatic coupling is stronger than for HCl scattering from Au, where the solid's work function is higher. HCl differs from other systems in that dissociation is possible over a low barrier. Vibrationally inelastic v = 1 → 2 transitions could not be seen when HCl (v = 1) collides with an Ag(111) surface. We suggest that scattering events, where HCl (v = 1) is subject to dynamical influences that increase its vibrational energy, lead efficiently to dissociation before the HCl (v = 2) molecule can escape the surface. This system appears to be an excellent candidate to study electronically nonadiabatic effects in dissociative adsorption. [ABSTRACT FROM AUTHOR]

CO adsorbed to NaCl(100) exhibits perhaps the weakest possible coupling between the adsorbate and solid. It is, therefore, an ideal system to observe the influence of adsorbate–adsorbate interactions on infrared absorption. In this work, we report polarized FTIR absorption spectra of CO/NaCl(100) as a function of coverage (0.02 ≤ θ ≤ 1 ML), where the coverage has been quantitatively determined by temperature-programmed desorption and molecular beam dosing. We extend a previous semi-empirical model designed to describe the screening of the local electric field due to dipole–dipole interactions in a CO monolayer. The extended model applies to sub-monolayer coverages and describes properly the electric field of the absorbed radiation at the vacuum–substrate interface. Fitting this model to coverage-dependent IR absorption data allows us to derive the vibrational and electronic polarizabilities [χv = 0.0435(14) Å3, χe = 3.30(36) Å3] and the integrated absorption cross section of 2.51(8) × 10−17 cm/molecule for an isolated CO molecule adsorbed at the NaCl (100) surface. The determined integrated absorption cross section is substantially smaller than that of gas phase CO. [ABSTRACT FROM AUTHOR]