Understanding the Photoinduced Desorption and Oxidation of CO on Ru(0001) Using a Neural Network Potential Energy Surface.

The study of ultrafast photoinduced dynamics of adsorbates on metal surfaces requires thorough investigation of laser-excited electrons and, in many cases, the highly excited surface lattice. While ab initio molecular dynamics with electronic friction and thermostats (Te, Tl)-AIMDEF addresses such complex modeling, it imposes severe computational costs, hindering quantitative comparison with experimental desorption probabilities. In order to bypass this limitation, we utilize the embedded atom neural network method to construct a potential energy surface (PES) for the coadsorption of CO and O on Ru(0001). Our results demonstrate that this PES not only reproduces the short-time ab initio dynamics but is also able to yield statistically significant data for long lasting trajectories that correlate well with experimental findings. Furthermore, the analysis of the laser-induced dynamics reveals the existence of a dynamic trapping state that acts as a precursor for CO desorption, and it is not observed under thermal conditions. Altogether, our results validate the underlying theoretical framework, providing robust support for the description of not only the photoinduced desorption but also the oxidation of CO in terms of nonequilibrated but thermal hot electrons and phonons.

Multicoverage Study of Femtosecond Laser-Induced Desorption of CO from Pd(111).

We study the strong coverage dependence of the femtosecond laser-induced desorption of CO from Pd(111) using molecular dynamics simulations that consistently include the effect of the laser-induced hot electrons on both the adsorbates and surface atoms. Adiabatic forces are obtained from a multicoverage neural network potential energy surface that we construct using data from density functional theory calculations for 0.33 and 0.75 monolayer (ML). Our molecular dynamics simulations performed for these two trained coverages and an additional intermediate coverage of 0.60 ML reproduce well the peculiarities of the experimental findings. The performed simulations also permit us to disentangle the relative role played by the excited electrons and phonons on the desorption process and discover interesting properties of the reaction dynamics as the relevance that the precursor physisorption well acquires during the dynamics as coverage increases.

Disentangling the role of electrons and phonons in the photoinduced CO desorption and CO oxidation on (O,CO)-Ru(0001).

The role played by electronic and phononic excitations in the femtosecond laser induced desorption and oxidation of CO coadsorbed with O on Ru(0001) is investigated using ab initio molecular dynamics with electronic friction. To this aim, simulations that account for both kind of excitations and that only consider electronic excitations are performed. Results for three different surface coverages are obtained. We unequivocally demonstrate that CO desorption is governed by phononic excitations. In the case of oxidation the low statistics does not allow to give a categorical answer. However, the analysis of the adsorbates kinetic energy gain and displacements strongly suggest that phononic excitations and surface distortion also play an important role in the oxidation process.

Photoinduced Desorption Dynamics of CO from Pd(111): A Neural Network Approach.

Modeling the ultrafast photoinduced dynamics and reactivity of adsorbates on metals requires including the effect of the laser-excited electrons and, in many cases, also the effect of the highly excited surface lattice. Although the recent ab initio molecular dynamics with electronic friction and thermostats, (Te,Tl)-AIMDEF [Alducin, M.; Phys. Rev. Lett. 2019, 123, 246802], enables such complex modeling, its computational cost may limit its applicability. Here, we use the new embedded atom neural network (EANN) method [Zhang, Y.; J. Phys. Chem. Lett. 2019, 10, 4962] to develop an accurate and extremely complex potential energy surface (PES) that allows us a detailed and reliable description of the photoinduced desorption of CO from the Pd(111) surface with a coverage of 0.75 monolayer. Molecular dynamics simulations performed on this EANN-PES reproduce the (Te,Tl)-AIMDEF results with a remarkable level of accuracy. This demonstrates the outstanding performance of the obtained EANN-PES that is able to reproduce available density functional theory (DFT) data for an extensive range of surface temperatures (90-1000 K); a large number of degrees of freedom, those corresponding to six CO adsorbates and 24 moving surface atoms; and the varying CO coverage caused by the abundant desorption events.

High-Dimensional Atomistic Neural Network Potential to Study the Alignment-Resolved O2 Scattering from Highly Oriented Pyrolytic Graphite.

A high dimensional and accurate atomistic neural network potential energy surface (ANN-PES) that describes the interaction between one O2 molecule and a highly oriented pyrolytic graphite (HOPG) surface has been constructed using the open-source package (aenet). The validation of the PES is performed by paying attention to static characteristics as well as by testing its performance in reproducing previous ab initio molecular dynamics simulation results. Subsequently, the ANN-PES is used to perform quasi-classical molecular dynamics calculations of the alignment-dependent scattering of O2 from HOPG. The results are obtained for 200 meV O2 molecules with different initial alignments impinging with a polar incidence angle with respect to the surface normal of 22.5° on a thermalized (110 and 300 K) graphite surface. The choice of these initial conditions in our simulations is made to perform comparisons to recent experimental results on this system. Our results show that the scattering of O2 from the HOPG surface is a rather direct process, that the angular distributions are alignment dependent, and that the final translational energy of end-on molecules is around 20% lower than that of side-on molecules. Upon collision with the surface, the molecules that are initially aligned perpendicular to the surface become highly rotationally excited, whereas a very small change in the rotational state of the scattered molecules is observed for the initial parallel alignments. The latter confirms the energy transfer dependence on the stereodynamics for the present system. The results of our simulations are in overall agreement with the experimental observations regarding the shape of the angular distributions and the alignment dependence of the in-plane reflected molecules.

Reactive and Nonreactive Scattering of HCl from Au(111): An Ab Initio Molecular Dynamics Study.

The HCl + Au(111) system has recently become a benchmark for highly activated dissociative chemisorption, which presumably is strongly affected by electron-hole pair excitation. Previous dynamics calculations, which were based on density functional theory at the generalized gradient approximation level (GGA-DFT) for the molecule-surface interaction, have all overestimated measured reaction probabilities by at least an order of magnitude. Here, we perform ab initio molecular dynamics (AIMD) and AIMD with electronic friction (AIMDEF) calculations employing a density functional that includes the attractive van der Waals interaction. Our calculations model the simultaneous and possibly synergistic effects of surface temperature, surface atom motion, electron-hole pair excitation, the molecular beam conditions of the experiments, and the van der Waals interaction on the reactivity. We find that reaction probabilities computed with AIMDEF and the SRP32-vdW functional still overestimate the measured reaction probabilities, by a factor 18 for the highest incidence energy at which measurements were performed (≈2.5 eV). Even granting that the experiment could have underestimated the sticking probability by about a factor three, this still translates into a considerable overestimation of the reactivity by the current theory. Likewise, scaled transition probabilities for vibrational excitation from ν = 1, j = 1 to ν = 2 are overestimated by the AIMDEF theory, by factors 3-8 depending on the initial conditions modeled. Energy losses to the surface and translational energy losses are, however, in good agreement with experimental values.

Electrons and Phonons Cooperate in the Laser-Induced Desorption of CO from Pd(111).

Femtosecond laser induced desorption of CO from a CO-covered Pd(111) surface is investigated with ab initio molecular dynamics with electronic friction that incorporates effects due to the excited electronic and phononic systems, as well as out-of-phase coadsorbate interactions. Our simulations show evidence of an important electron-phonon synergy in promoting CO desorption that has largely been neglected in other similar systems. At the saturated coverage of 0.75 ML, effects due to CO-CO interadsorbate energy exchange are also important. Our dynamics simulations, in concert with site-specific desorption energy calculations, allow us to understand the large coverage dependence of the desorption yields observed in experiments.

Dynamics of N2 sticking on W(100): the decisive role of van der Waals interactions.

The reactive dynamics of N2 on W(100) has been investigated by means of quasi-classical trajectory calculations using an interpolated six-dimensional potential energy surface (PES) based on density functional theory energies obtained employing the vdW-DF2 functional. The dynamics are compared to those obtained using the PW91 functional and to experimental data. The results show that the new PES provides a significant improvement in the description of the reactivity in this system. We show that the long standing problem that constituted the large qualitative disagreement between the simulations performed with the PW91-PES and the experiments was due to the presence of energy barriers in the entrance channel that disappear when vdW forces are accounted for.

Electron-hole pair effects in methane dissociative chemisorption on Ni(111).

The dissociative chemisorption of methane on metal surfaces has attracted much attention in recent years as a prototype of gas-surface reactions in understanding the mode specific and bond selective chemistry. In this work, we systematically investigate the influence of electron-hole pair excitations on the dissociative chemisorption of CH4/CH3D/CHD3 on Ni(111). The energy dissipation induced by surface electron-hole pair excitations is modeled as a friction force introduced in the generalized Langevin equation, in which the independent atomic friction coefficients are determined within the local-density friction approximation. Quasi-classical trajectory calculations for CH4/CH3D/CHD3 have been carried out on a recently developed twelve-dimensional potential energy surface. Comparing the dissociation probabilities obtained with and without friction, our results clearly indicate that the electron-hole pair effects are generally small, both on absolute reactivity of each vibrational state and on the mode specificity and bond selectivity. Given similar observations in both water and methane dissociation processes, we conclude that electron-hole pair excitations would not play an important role as long as the reaction is direct and the interaction time between the molecule and metal electrons is relatively short.

Electronic Friction-Based Vibrational Lifetimes of Molecular Adsorbates: Beyond the Independent-Atom Approximation.

We assess the accuracy of vibrational damping rates of diatomic adsorbates on metal surfaces as calculated within the local-density friction approximation (LDFA). An atoms-in-molecules (AIM) type charge partitioning scheme accounts for intramolecular contributions and overcomes the systematic underestimation of the nonadiabatic losses obtained within the prevalent independent-atom approximation. The quantitative agreement obtained with theoretical and experimental benchmark data suggests the LDFA-AIM scheme as an efficient and reliable approach to account for electronic dissipation in ab initio molecular dynamics simulations of surface chemical reactions.