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 wave1. 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 rates2. 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 surface3,4, 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.

Transporting and concentrating vibrational energy to promote isomerization.

Visible-light absorption and transport of the resultant electronic excitations to a reaction centre through Förster resonance energy transfer1-3 (FRET) are critical to the operation of biological light-harvesting systems4, and are used in various artificial systems made of synthetic dyes5, polymers6 or nanodots7,8. The fundamental equations describing FRET are similar to those describing vibration-to-vibration (V-V) energy transfer9, and suggest that transport and localization of vibrational energy should, in principle, also be possible. Although it is known that vibrational excitation can promote reactions10-16, 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) surface17. Here we build on that work to show that the isomerization reaction proceeds more efficiently with a thick 12C16O overlayer that absorbs more mid-infrared photons and transports the resultant vibrational excitations by V-V energy transfer to a 13C18O-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.

Spiers Memorial Lecture: New directions in molecular scattering.

The field of molecular scattering is reviewed as it pertains to gas-gas as well as gas-surface chemical reaction dynamics. We emphasize the importance of collaboration of experiment and theory, from which new directions of research are being pursued on increasingly complex problems. We review both experimental and theoretical advances that provide the modern toolbox available to molecular-scattering studies. We distinguish between two classes of work. The first involves simple systems and uses experiment to validate theory so that from the validated theory, one may learn far more than could ever be measured in the laboratory. The second class involves problems of great complexity that would be difficult or impossible to understand without a partnership of experiment and theory. Key topics covered in this review include crossed-beams reactive scattering and scattering at extremely low energies, where quantum effects dominate. They also include scattering from surfaces, reactive scattering and kinetics at surfaces, and scattering work done at liquid surfaces. The review closes with thoughts on future promising directions of research.

Identification of reaction intermediates in the decomposition of formic acid on Pd.

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.

Vibrational energy transfer in collisions of molecules with metal surfaces.

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.

Vibrationally Mode-Specific Molecular Energy Transfer to Surface Electrons in Metastable Formaldehyde Scattering from Cesium-Covered Au(111).

Nonadiabatic interaction of adsorbate nuclear motion with the continuum of electronic states is known to affect the dynamics of chemical reactions at metal surfaces. A large body of work has probed the fundamental mechanisms of such interactions for atomic and diatomic molecules at surfaces. In polyatomic molecules, the possibility of mode-specific damping of vibrational motion due to the effects of electronic friction raises the question of whether such interactions could profoundly affect the outcome of chemistry at surfaces by selectively removing energy from a particular intramolecular adsorbate mode. However, to date, there have not been any fundamental experiments demonstrating nonadiabatic electron-vibration coupling in a polyatomic molecule at a surface. In this work, we scatter excited metastable formaldehyde and formaldehyde-d2 from a low work function surface and detect ejected exoelectrons that accompany molecular relaxation. The exoelectron ejection efficiency exhibits a strong dependence on the vibrational mode that is excited: out-of-plane bending excitation (ν4) leads to significantly more exoelectrons than does CO stretching excitation (ν2). The results provide clear evidence for mode-specific energy transfer from vibration to surface electrons.

Velocity-resolved kinetics of site-specific carbon monoxide oxidation on platinum surfaces.

Catalysts are widely used to increase reaction rates. They function by stabilizing the transition state of the reaction at their active site, where the atomic arrangement ensures favourable interactions 1 . However, mechanistic understanding is often limited when catalysts possess multiple active sites-such as sites associated with either the step edges or the close-packed terraces of inorganic nanoparticles2-4-with distinct activities that cannot be measured simultaneously. An example is the oxidation of carbon monoxide over platinum surfaces, one of the oldest and best studied heterogeneous reactions. In 1824, this reaction was recognized to be crucial for the function of the Davy safety lamp, and today it is used to optimize combustion, hydrogen production and fuel-cell operation5,6. The carbon dioxide products are formed in a bimodal kinetic energy distribution7-13; however, despite extensive study 5 , it remains unclear whether this reflects the involvement of more than one reaction mechanism occurring at multiple active sites12,13. Here we show that the reaction rates at different active sites can be measured simultaneously, using molecular beams to controllably introduce reactants and slice ion imaging14,15 to map the velocity vectors of the product molecules, which reflect the symmetry and the orientation of the active site 16 . We use this velocity-resolved kinetics approach to map the oxidation rates of carbon monoxide at step edges and terrace sites on platinum surfaces, and find that the reaction proceeds through two distinct channels11-13: it is dominated at low temperatures by the more active step sites, and at high temperatures by the more abundant terrace sites. We expect our approach to be applicable to a wide range of heterogeneous reactions and to provide improved mechanistic understanding of the contribution of different active sites, which should be useful in the design of improved catalysts.

Superconducting single-photon detectors in the mid-infrared for physical chemistry and spectroscopy.

Applications of vibrational spectroscopy throughout the field of physical chemistry are limited by detectors with poor temporal resolution, low detection efficiency, and high background levels. Up to now, the field has relied upon detectors based on semiconducting materials with small bandgaps, which unavoidably leads to a compromise between good spectral response and noise at long wavelengths. However, a revolution in mid-infrared light detection is underway based on the interactions of photons with superconducting materials, which function under fundamentally different operating principles. Superconducting detectors were first used to detect light at shorter wavelengths. However, recent developments in their sensitivity toward mid-infrared wavelengths up to 10 µm provide new opportunities for applications in molecular science, such as infrared emission experiments, exoplanet spectroscopy and single molecule microscopy. In this tutorial review, we provide background information needed for the non-expert in superconducting light detection to apply these devices in the field of mid-infrared molecular spectroscopy. We present and compare the detection mechanisms and current developments of three types of superconducting detectors: superconducting nanowire single-photon detectors (SNSPDs), transition edge sensors (TESs), and microwave kinetic inductance detectors (MKIDs). We also highlight existing applications of SNSPDs for laser-induced infrared fluorescence experiments and discuss their potential for other molecular spectroscopy applications. Ultimately, superconducting infrared detectors have the potential to approach the sensitivity and characteristics of established single-photon detectors operating in the UV/Vis region, which have existed for almost a century and become an indispensable tool within the field of physical chemistry.

Highly Rotationally Excited N2 Reveals Transition-State Character in the Thermal Decomposition of N2O on Pd(110).

We employ time-slice and velocity map ion imaging methods to explore the quantum-state resolved dynamics in thermal N2O decomposition on Pd(110). We observe two reaction channels: a thermal channel that is ascribed to N2 products initially trapped at surface defects and a hyperthermal channel involving a direct release of N2 to the gas phase from N2O adsorbed on bridge sites oriented along the [001] azimuth. The hyperthermal N2 is highly rotationally excited up to J = 52 (v″ = 0) with a large average translational energy of 0.62 eV. Between 35 and 79% of the estimated barrier energy (1.5 eV) released upon dissociation of the transition state (TS) is taken up by the desorbed hyperthermal N2. The observed attributes of the hyperthermal channel are interpreted by post-transition-state classical trajectories on a density functional theory-based high-dimensional potential energy surface. The energy disposal pattern is rationalized by the sudden vector projection model, which attributes to unique features of the TS. Applying detailed balance, we predict that in the reverse Eley-Rideal reaction, both N2 translational and rotational excitation promote N2O formation.

Binding Energy and Diffusion Barrier of Formic Acid on Pd(111).

Velocity-resolved kinetics is used to measure the thermal rate of formic acid desorption from Pd(111) between 228 and 273 K for four isotopologues: HCOOH, HCOOD, DCOOH, DCOOD. Upon molecular adsorption, formic acid undergoes decomposition to CO2 and H2 and thermal desorption. To disentangle the contributions of individual processes, we implement a mass-balance-based calibration procedure from which the branching ratio between desorption and decomposition for formic acid is determined. From experimentally derived elementary desorption rate constants, we obtain the binding energy 639 ± 8 meV and the diffusion barrier 370 ± 130 meV using the detailed balance rate model (DBRM). The DBRM explains the observed kinetic isotope effects.

Quantum and classical molecular dynamics for H atom scattering from graphene.

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.

Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-Atoms.

A detailed velocity-resolved kinetics study of NH3 thermal desorption rates from p(2 × 2) O/Pt(111) is presented. We find a large reduction in the NH3 desorption rate due to adsorption of O-atoms on Pt(111). A physical model describing the interactions between adsorbed NH3 and O-atoms explains these observations. By fitting the model to the derived desorption rate constants, we find an NH3 stabilization on p(2 × 2) O/Pt(111) of 0.147-0.014+0.023 eV compared to Pt(111) and a rotational barrier of 0.084-0.022+0.049 eV, which is not present on Pt(111). The model also quantitatively predicts the steric hindrance of NH3 diffusion on Pt(111) due to co-adsorbed O-atoms. The derived diffusion barrier of NH3 on p(2 × 2) O/Pt(111) is 1.10-0.13+0.22 eV, which is 0.39-0.14+0.22 eV higher than that on pristine Pt(111). We find that Perdew Burke Ernzerhof (PBE) and revised Perdew Burke Ernzerhof (RPBE) exchange-correlation functionals are unable to reproduce the experimentally observed NH3-O adsorbate-adsorbate interactions and NH3 binding energies at Pt(111) and p(2 × 2) O/Pt(111), which indicates the importance of dispersion interactions for both systems.

Effective medium theory for bcc metals: electronically non-adiabatic H atom scattering in full dimensions.

We report a newly derived Effective Medium Theory (EMT) formalism for bcc metals and apply it for the construction of a full-dimensional PES for H atoms interacting with molybdenum (Mo) and tungsten (W). We construct PESs for the (111) and (110) facets of both metals. The EMT-PESs have the advantage that they automatically provide the background electron density on the fly which makes incorporation of ehp excitation within the framework of electronic friction straightforward. Using molecular dynamics with electronic friction (MDEF) with these new PESs, we simulated 2.76 eV H atoms scattering and adsorption. The large energy losses at a surface temperature of 300 K is very similar those seen for H atom scattering from the late fcc metals and is dominated by ehp excitation. We see significant differences in the scattering from different surface facets of the same metal. For the (110) facet, we see strong evidence of sub-surface scattering, which should be observable in experiment and we predict the best conditions for observing this novel type of scattering process. At low temperatures the MD simulations predict that H atom scattering is surface specific due to the reduced influence of the random force.

H atom scattering from W(110): A benchmark for molecular dynamics with electronic friction.

Molecular dynamics with electronic friction (MDEF) at the level of the local density friction approximation (LDFA) has been applied to describe electronically non-adiabatic energy transfer accompanying H atom collisions with many solid metal surfaces. When implemented with full dimensional potential energy and electron density functions, excellent agreement with experiment is found. Here, we compare the performance of a reduced dimensional MDEF approach involving a simplified description of H atom coupling to phonons to that of full dimensional MDEF calculations known to yield accurate results. Both approaches give remarkably similar results for H atom energy loss distributions with a 300 K W(110) surface. At low surface temperature differences are seen; but, quantities like average energy loss are still accurately reproduced. Both models predict similar conditions under which H atoms that have penetrated into the subsurface regions could be observed in scattering experiments.

Stereodynamics of adiabatic and non-adiabatic energy transfer in a molecule surface encounter.

Molecular energy transfer and reactions at solid surfaces depend on the molecular orientation relative to the surface. While such steric effects have been largely understood in electronically adiabatic processes, the orientation-dependent energy transfer in NO scattering from Au(111) was complicated by electron-mediated nonadiabatic effects, thus lacking a clear interpretation and posing a great challenge for theories. Herein, we investigate the stereodynamics of adiabatic and nonadiabatic energy transfer via molecular dynamics simulations of NO(v = 3) scattering from Au(111) using realistic initial orientation distributions based on accurate neural network fitted adiabatic potential energy surface and electronic friction tensor. Our results reproduce the observed stronger vibrational relaxation for N-first orientation and enhanced rotational rainbow for O-first orientation, and demonstrate how adiabatic anisotropic interactions steer molecules into the more attractive N-first orientation to experience more significant energy transfer. Remaining disagreements with experiment suggest the direction for further developments of nonadiabatic theories for gas-surface scattering.

Velocity map images of desorbing oxygen from sub-surface states of Rh(111).

We combine velocity map imaging (VMI) with temperature-programmed desorption (TPD) experiments to record the angular-resolved velocity distributions of recombinatively-desorbing oxygen from Rh(111). We assign the velocity distributions to desorption from specific surface and sub-surface states by matching the recorded distributions to the desorption temperature. These results provide insight into the recombinative desorption mechanisms and the availability of oxygen for surface-catalyzed reactions.

Application of an Event-Based Camera for Real-Time Velocity Resolved Kinetics.

We describe here the application of an inexpensive event-based/neuromorphic camera in an ion imaging experiment operated at 1 kHz detection rate to study real-time velocity-resolved kinetics of thermal desorption. Such measurements involve a single gas pulse to initiate a time-dependent desorption process and a high repetition rate laser, where each pulse of the laser is used to produce an ion image. The sequence of ion images allows the time dependence of the desorption flux to be followed in real time. In previous work where a conventional framing camera was used, the large number of megapixel-sized images required data transfer and storage rates of up to 16 GB/s. This necessitated a large onboard memory that was quickly filled and limited continuous measurement to only a few seconds. Read-out of the memory became the bottleneck to the rate of data acquisition. We show here that since most pixels in each ion image contain no data, the data rate can be dramatically reduced by using an event-based/neuromorphic camera. The data stream is thus reduced to the intensity and location information on the pixels that are lit up by each ion event together with a time-stamp indicating the arrival time of an ion at the detector. This dramatically increases the duty cycle of the method and provides insights for the execution of other high rep-rate ion imaging experiments.

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.

Generation of Sub-nanosecond H Atom Pulses for Scattering from Single-Crystal Epitaxial Graphene.

Pulsed molecular beams allow high-density gas samples to be cooled to low internal temperatures and to produce narrow speed distributions. They are particularly useful in combination with pulsed-laser-based detection schemes and have also been used as pump pulses in pump-probe experiments with neutral matter. The mechanical response of pulsed valves and chopper wheels limits the duration of these pulses typically to about 10-100 µs. Bunch compression photolysis has been proposed as a means to produce atomic pulses shorter than 1 ns─an experimental capability that would allow new measurements to be made on chemical systems. This technique employs a spatially chirped femtosecond duration photolysis pulse that produced an ensemble of H atom photoproducts that rebunches into a short pulse downstream. To date, this technique could not produce strong enough beams to allow new experiments to be carried out. In this paper, we report production of pulsed H atom beams consistent with a 700 ps pulse duration and with sufficient intensity to carry out differentially resolved inelastic H scattering experiments from a graphene surface. We observe surprisingly narrow angular distributions for H atoms incident normal to the surface. At low incidence energies quasi-elastic scattering dominates, and at high incidence energy we observe a strongly inelastic scattering channel. These results provide the basis for future experiments where the H atoms synchronously collide with a pulsed-laser-excited surface.

Kinetics of NH3 Desorption and Diffusion on Pt: Implications for the Ostwald Process.

We report accurate time-resolved measurements of NH3 desorption from Pt(111) and Pt(332) and use these results to determine elementary rate constants for desorption from steps, from (111) terrace sites and for diffusion on (111) terraces. Modeling the extracted rate constants with transition state theory, we find that conventional models for partition functions, which rely on uncoupled degrees of freedom (DOFs), are not able to reproduce the experimental observations. The results can be reproduced using a more sophisticated partition function, which couples DOFs that are most sensitive to NH3 translation parallel to the surface; this approach yields accurate values for the NH3 binding energy to Pt(111) (1.13 ± 0.02 eV) and the diffusion barrier (0.71 ± 0.04 eV). In addition, we determine NH3's binding energy preference for steps over terraces on Pt (0.23 ± 0.03 eV). The ratio of the diffusion barrier to desorption energy is ∼0.65, in violation of the so-called 12% rule. Using our derived diffusion/desorption rates, we explain why established rate models of the Ostwald process incorrectly predict low selectivity and yields of NO under typical reactor operating conditions. Our results suggest that mean-field kinetics models have limited applicability for modeling the Ostwald process.