Inelastic scattering of H and D atoms from the (111) surfaces of six fcc transition metals (Au, Pt, Ag, Pd, Cu, and Ni) was investigated, and in each case, excitation of electron-hole pairs dominates the inelasticity. The results are very similar for all six metals. Differences in the average kinetic energy losses between metals can mainly be attributed to different efficiencies in the coupling to phonons due to the different masses of the metal atoms. The experimental observations can be reproduced by molecular dynamics simulations based on full-dimensional potential energy surfaces and including electronic excitations by using electronic friction in the local density friction approximation. The determining factors for the energy loss are the electron density at the surface, which is similar for all six metals, and the mass ratio between the impinging atoms and the surface atoms. Details of the electronic structure of the metal do not play a significant role. The experimentally validated simulations are used to explore sticking over a wide range of incidence conditions. We find that the sticking probability increases for H and D collisions near normal incidence-consistent with a previously reported penetration-resurfacing mechanism. The sticking probability for H or D on any of these metals may be represented as a simple function of the incidence energy, E, metal atom mass, M, and incidence angle, 𝜗. S=(S+a⋅E+b⋅M)*(1-h(𝜗-c)(1-cos(𝜗-c))), where h is the Heaviside step function and for H, S = 1.081, a = -0.125 eV, b=-8.40⋅10 u, c = 28.88°, d = 1.166 eV, and e = 0.442 eV; whereas for D, S = 1.120, a = -0.124 eV, b=-1.20⋅10 u, c = 28.62°, d = 1.196 eV, and e = 0.474 eV.

The photodissociation dynamics of CH 3 I and CH 2 ClI at 272 nm were investigated by time-resolved Coulomb explosion imaging, with an intense non-resonant 815 nm probe pulse. Fragment ion momenta over a wide m/z range were recorded simultaneously by coupling a velocity map imaging spectrometer with a pixel imaging mass spectrometry camera. For both molecules, delay-dependent pump-probe features were assigned to ultraviolet-induced carbon-iodine bond cleavage followed by Coulomb explosion. Multi-mass imaging also allowed the sequential cleavage of both carbon-halogen bonds in CH 2 ClI to be investigated. Furthermore, delay-dependent relative fragment momenta of a pair of ions were directly determined using recoil-frame covariance analysis. These results are complementary to conventional velocity map imaging experiments and demonstrate the application of time-resolved Coulomb explosion imaging to photoinduced real-time molecular motion.

Due to its element-and site-specificity, inner-shell photoelectron spectroscopy is a widely used technique to probe the chemical structure of matter. Here we show that time-resolved innershell photoelectron spectroscopy can be employed to observe ultrafast chemical reactions and the electronic response to the nuclear motion with high sensitivity. The ultraviolet dissociation of iodomethane (CH3I) is investigated by ionization above the iodine 4d edge, using time-resolved inner-shell photoelectron and photoion spectroscopy. The dynamics observed in the photoelectron spectra appear earlier and are faster than those seen in the iodine fragments. The experimental results are interpreted using crystal field and spin-orbit configuration interaction calculations, and demonstrate that time-resolved inner-shell photoelectron spectroscopy is a powerful tool to directly track ultrafast structural and electronic transformations in gas-phase molecules. arXiv:1901.08937v1 [physics.chem-ph] 25 Jan 2019 0 +) [fs] Energy [eV] J=5/2, J =5/2 J=3/2, J =3/2 J=5/2, J =3/2 J=3/2, J =1/2 J=5/2, J =1/2 z z z z z

Polycyclic aromatic hydrocarbons (PAHs) play an important role in interstellar chemistry and are subject to high energy photons that can induce excitation, ionization, and fragmentation. Previous studies have demonstrated electronic relaxation of parent PAH monocations over 10–100 femtoseconds as a result of beyond-Born-Oppenheimer coupling between the electronic and nuclear dynamics. Here, we investigate three PAH molecules: fluorene, phenanthrene, and pyrene, using ultrafast XUV and IR laser pulses. Simultaneous measurements of the ion yields, ion momenta, and electron momenta as a function of laser pulse delay allow a detailed insight into the various molecular processes. We report relaxation times for the electronically excited PAH*, PAH+* and PAH2+* states, and show the time-dependent conversion between fragmentation pathways. Additionally, using recoil-frame covariance analysis between ion images, we demonstrate that the dissociation of the PAH2+ ions favors reaction pathways involving two-body breakup and/or loss of neutral fragments totaling an even number of carbon atoms.

The dynamics following laser-induced molecular photodissociation of gas-phase CH 2 BrI at 271.6 nm were investigated by time-resolved Coulomb explosion imaging using intense near-IR femtosecond laser pulses. The observed delay-dependent photofragment momenta reveal that CH 2 BrI undergoes C-I cleavage, depositing 65.6% of the available energy into internal product states, and that absorption of a second UV photon breaks the C-Br bond of CH 2 Br. Simulations confirm that this mechanism is consistent with previous data recorded at 248 nm, demonstrating the sensitivity of Coulomb explosion imaging as a real-time probe of chemical dynamics.2

We report vibrational excitation of CO from its ground (v = 0) to first excited (v = 1) vibrational state in collision with Au(111) at an incidence energy of translation of E(I) = 0.45 eV. Unlike past work, we can exclude an excitation mechanism involving temporary adsorption on the surface followed by thermalization and desorption. The angular distributions of the scattered CO molecules are narrow, consistent with direct scattering occurring on a sub-ps time scale. The absolute excitation probabilities are about 3% of those expected from thermal accommodation. The surface temperature dependence of excitation, which was measured between 373 and 973 K, is Arrhenius-like with an activation energy equal to the energy required for vibrational excitation. Our measurements are consistent with a vibrational excitation mechanism involving coupling of thermally excited electron-hole pairs of the solid to CO vibration.

Ultrafast laser pump-probe methods allow chemical reactions to be followed in real time, and have provided unprecedented insight into fundamental aspects of chemical reactivity. While evolution of the electronic structure of the system under study is evident from changes in the observed spectral signatures, information on rearrangement of the nuclear framework is generally obtained indirectly. Disentangling contributions to the signal arising from competing photochemical pathways can also be challenging. Here we introduce the new technique of three-dimensional covariance-map Coulomb explosion imaging, which has the potential to provide complete three-dimensional information on molecular structure and dynamics as they evolve in real time during a gas-phase chemical reaction. We present first proof-of-concept data from recent measurements on CF3I. Our approach allows the contributions from competing fragmentation pathways to be isolated and characterised unambiguously, and is a promising route to enabling the recording of ‘molecular movies’ for a wide variety of gas-phase chemical processes.

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