We quantitatively evaluate the contribution of electron-hole pair excitations to the reactive dynamics of H 2 on Cu(110) and N 2 on W(110), including the six dimensionality of the process in the entire calculation. The interaction energy between molecule and surface is represented by an ab initio six-dimensional potential energy surface. Electron friction coefficients are calculated with density functional theory in a local density approximation. Contrary to previous claims, only minor differences between the adiabatic and nonadiabatic results for dissociative adsorption are found. Our calculations demonstrate the validity of the adiabatic approximation to analyze adsorption dynamics in these two representative systems. DOI: 10.1103/PhysRevLett.100.116102 PACS numbers: 82.65.+r, 34.35.+a, 68.49.Df, 82.20.Kh The adiabatic Born-Oppenheimer approximation is ubiquitous in the theoretical study of elementary reactive processes at surfaces. Still, there is ample experimental evidence of electronic excitations associated to gas or surface reactions, that can potentially break down the applicability of the adiabatic approach. Electron-hole pairs appear, for instance, in the detection of chemicurrents during the chemisorption of gas-phase species on thin metal films [1,2], as well as in the measurement of electron emission following the scattering of molecules in highlyexcited vibrational states on metal surfaces [3,4]. Although the existence of energy dissipation through electron-hole (e-h) pair excitations is widely accepted, there is not a definite quantitative answer on the role of electronic excitations in the adsorption and reaction rates of diatomic molecules at metal surfaces [5].Laursen et al. [6] predicted that e-h pair excitations should alter substantially the adsorption dynamics of H 2 in Cu (110). Contravening this prediction, full sixdimensional (6D) adiabatic calculations of the dynamics based on an ab initio potential energy surface have been shown to provide a good description of the experimental results on this system [7]. Measurements of the dissociative adsorption and diffractive scattering of H 2 on Pt(111) are reasonably well described within the adiabatic approximation as well [8]. For heavier molecules, it was claimed that strong energy dissipation effects due to the excitation of e-h pairs are responsible for the strong disagreement between (adiabatic) theoretical and experimental sticking coefficients for N 2 on Ru(0001) [9,10]. Díaz et al. [11] showed afterwards that when the full dimensionality of the process is taken into account, adiabatic calculations are much closer to experiments. This result suggests that nonadiabatic effects might be smaller than previously predicted. Still, the lack of a theoretical calculation, based on state-of-the-art interaction potentials, that explicitly includes the e-h pair excitation channel and the full dimensionality of the process keeps this controversy open.In this Letter, we evaluate the contribution of e-h pair excitations to the dissociative adsorp...

While, at the same time, the correlated momenta of the entangled electron pair continue to exhibit quantum interference.

We study the dynamics of transient hot H atoms on Pd(100) that originated from dissociative adsorption of H 2 . The methodology developed here, denoted AIMDEF, consists of ab initio molecular dynamics simulations that include a friction force to account for the energy transfer to the electronic system. We find that the excitation of electron-hole pairs is the main channel for energy dissipation, which happens at a rate that is five times faster than energy transfer into Pd lattice motion. Our results show that electronic excitations may constitute the dominant dissipation channel in the relaxation of hot atoms on surfaces. DOI: 10.1103/PhysRevLett.112.103203 PACS numbers: 68.43.-h, 34.35.+a, 34.50.Bw, 82.20.Gk Electron-hole (e-h) pair excitations are an unquestioned efficient energy drain in the interaction of fast atoms with solids and surfaces [1][2][3][4]. In contrast, the relevance of this dissipation channel in gas-surface interactions that involve energies up to a few eV is not so clear. It depends not only on the specific system, but also on the elementary process considered, as shown by different studies on scattering [5][6][7][8][9][10][11][12] and adsorption [6,[13][14][15][16][17][18][19][20][21][22][23][24][25][26] of atoms and molecules on surfaces. Low-energy e-h pair excitations have been detected as chemicurrents on Schottky diode devices during the chemisorption of atomic and molecular species on metals [13][14][15]. The correlation found between chemicurrent intensities and adsorption energies is a strong indication that a large fraction of the energy dissipated in both the dissociative and nondissociative adsorption processes is used to excite e-h pairs. However, this strongly contrasts with examples showing that the dissociative adsorption is reasonably well described within the electronically adiabatic approach, which neglects the coupling between electronic excitations and the nuclear motion [6,[18][19][20]23,25], and that the effect of electronic energy dissipation seems negligible [21,24,26]. Therefore, a question that is raised here is at what stage of the dissociative adsorption process e-h pair excitations do become relevant.In a typical adsorption event, the incoming gas species gain additional kinetic energy when entering the attractive adsorption well. In the particular case of dissociative adsorption, this energy gain can lead to the formation of so-called "hot" atoms or fragments, with energies much larger than the corresponding thermal energies of the substrate atoms. The formed hot species will then propagate along the surface until they dissipate the excess kinetic energy and finally accommodate at a stable adsorption position. This stage of the dissociative adsorption process, where the relevance of e-h pair excitations has been traditionally neglected, is the focus of the present work.In this Letter we show that while e-h pair excitation may not be relevant on the molecule-bond-breaking time scale, it is an efficient dissipative channel in the subsequent relaxation of the...

Juaristi et al. Reply: In the preceding Comment [1] on our recent Letter [2], Luntz et al. claim that their results show that the local density approximation for electronic friction (LDAF) is in general not reliable for estimating the electronic friction for molecules on metal surfaces. This is an unfounded statement based on very limited information.Our LDAF calculation for the friction coefficient involves at most two further approximations as compared to those involved in the model used by Luntz et al.. (i) First, a local approximation for the electronic density is used. This is acknowledged to be a reasonable approximation. The LDAF was shown to be appropriate for calculations of the friction coefficient for atoms in metal surfaces, incidentally by some of the authors of the comment [3]. (ii) An additional approximation is that two-center effects are disregarded. Two-center effects were shown not to change the order of magnitude in the case of H 2 [4], but no studies in other systems have been performed to our knowledge.

However, despite 80 years of theoretical attention, near exact calculations for such systems are only available for bound states. On the experimental side, the tests of these calculations are largely based upon level energies or single particle momentum 3 distributions. Very promising and challenging new classes of experiments are those which achieve a complete description of the outcome following the excitation of the ground state to an unbound continuum. The momenta, i.e. the set of vectors, of all the fragments of an atom or molecule break-up can be measured in coincidence with high precision using state-of-the-art imaging and timing techniques [16]. These asymptotic many-particle momentum distributions are determined by the interaction inducing the fragmentation, the bound initial state from which it emerged, and the interactions between the outgoing particles. Thus it is useful to the experimentalist to keep the interaction process as simple as possible and to choose a geometry where final state interactions are negligible or under control. In the present study we used the absorption of a single photon to fragment the deuterium molecule: hν + D 2 → 2 e -+ 2 d + Due to their heavy masses, the initial motion of the nuclei in the continuum can be assumed the same as in the ground state at the instant of the electronic transition (Born Oppenheimer approximation). Once the electrons have left the system, the motion of the nuclei is solely determined by their Coulomb repulsion; they accelerate to a Kinetic Energy Release (KER) which corresponds to the Coulomb potential associated with their initial separation. Quantum mechanically one maps the nuclear vibrational wave-function onto the Coulomb potential to yield a KER spectrum. Inverting this process determines the squared nuclear vibrational wave-function from the measured KER spectrum [17]. Furthermore, by selecting events that occur within a fixed subregion in the KER spectrum, one samples molecules for which the corresponding internuclear distance is defined much more precisely than the full extent of the initial nuclear wave-function. This allows us to show how the electronic continuum momentum distribution depends on the inter-nuclear separation in the molecule and its orientation with respect to the photon polarization. [18,19,20,21]. In brief, inside our momentum spectrometer, a supersonic D 2 -gas jet was crossed with the linear polarized photon beam from the LBNL Advanced Light Source (D 2 provides a higher target density than a comparable H 2 gas jet and data less contaminated by random coincidences from background H 2 O). The electrons and ions created in the intersection of the photons with

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A comprehensive analysis of the stopping power of antiprotons and negative muons in He and gas targets for projectile velocities (equivalent antiproton energies) ranging from about 0.1 to 10 au (0.25 keV to 2.5 MeV) is performed. Recent experimental data are contrasted with theoretical results obtained from different approaches. The electronic stopping power is evaluated within the coupled-state atomic-orbital method and the distorted-wave Born approximation as well as, for low projectile velocities, within a generalized adiabatic-ionization model that takes into account collisional-broadening effects. The departure of the antiproton stopping power from the proton stopping power (`Barkas effect'), observed for intermediate projectile velocities, is discussed. The contribution to the stopping power arising from energy transfer to the translational degrees of freedom of the target system (`nuclear stopping') is evaluated. Our analysis results in a good understanding of the stopping mechanisms of negative heavy particles in gases, in particular in He. Discrepancies between theory and experiment in the case are attributed to effects of the molecular structure of the target.

The six-dimensional potential energy surface for the dissociation of N 2 molecules on the W͑110͒ surface has been determined by density functional calculations and interpolated using the corrugation reducing procedure. Examination of the resulting six-dimensional potential energy surface shows that nonactivated paths are available for dissociation. In spite of this, the dissociation probability goes to a very small value when the impact energy goes to zero and increases with increasing energy, a behavior usually associated with activated systems. Statistics on the dynamics indicate that this unconventional result is a consequence of the characteristics of the potential energy surface at long distances. Furthermore, two distinct channels are identified in the dissociation process, namely, a direct one and an indirect one. The former is responsible for dissociation at high energies. The latter, which includes long-lasting dynamic trapping in the vicinity of a potential well above the W top position, is the leading mechanism at low and intermediate energies.