Survival of rotational alignment in H-2 scattering from Si(100)

We report a state-prepared, state-resolved study of rotational scattering of a diatomic molecule from a solid surface. Specifically, H-2 molecules with 80 meV kinetic energy are rotationally aligned in the j = 3 rotational state via stimulated Raman pumping and then scattered from a Si(100) surface at normal incidence. The rotational alignment of the scattered molecules is determined by measuring, for both the incident and scattered molecules, the ionization yield of a probe laser, tuned to selectively ionize molecules in the j = 3 rotation level, as the probe laser polarization is rotated. The measurement is performed for two initial rotational alignments: a "helicoptering " alignment with the bonds constrained to lie primarily parallel to the surface and a "cartwheeling " alignment with the bonds lying primarily normal to the surface. For both initial alignments, the modulation of the probe ionization yield with laser polarization for the scattered molecules is pronounced, although significantly weaker than the modulation measured for the incident molecules. This indicates a significant modification but not a complete elimination of the initial alignment. The modulation is found to be stronger for the scattered molecules originating in the cartwheeling alignment than for the helicoptering alignment. These results contribute toward an improved understanding of the role of rotational motion in molecule-surface dynamics.

State-to-state surface scattering of methane studied by bolometric infrared laser tagging detection

Bo-Jung Chen

State-to-state molecule/surface scattering experiments prepare the incident molecules in a specific quantum state and measure the quantum state distribution of the scattered molecules. The comparison of state resolved experiments with theory can serve as stringent tests of the molecule/surface interaction potential and of the scattering dynamics. The overall motivation is to develop a predictive understanding of the molecule/surface interactions and reactions needed for the understanding and optimization of heterogeneous catalysis. In this thesis, I describe the design characterization, and first applications of a new apparatus, dedicated to performing state-to-state surfaces scattering using the bolometric infrared laser tagging detection (BILT). An important advantage of the BILT detection method over other state-resolved detection techniques such as resonant multi-photon ionization (REMPI), is its applicability to any molecule with an infrared active vibrational mode and a rotationally resolved vibrational gas phase spectrum. For example, BILT detection can be used to detect important molecules such as methane and carbon dioxide for which REMPI detection is not possible. Our new state-to-state scattering machine features a liquid helium-cooled bolometer detector installed on a rotatable lid allowing independent variation of the incident and the scattering angle. With this capability, one can study energy transfer such as the conversion of translational to rotational or vibrational energy as well as vibrational energy redistribution for molecules colliding with a well-defined single crystal surface at a wide variety of scattering geometry. To demonstrate the capabilities of the BILT machine, I studied the rotationally inelastic scattering of CH4 from Ni(111). The results show that rotational excitation depends not only on the kinetic energy along the surface normal but also on the parallel component although with lower efficiency. The extent of rotational excitation is found to increase with increasing surface temperature. The conversion efficiency appears to be higher for low velocity component normal to the surface. The observations indicate a mechanism of rotational excitation by phonon annihilation with the probability related to the relative velocity of the incoming molecules and surface atoms. Using the experimentally determined formula which takes into account the conversion efficiency of the normal, the parallel component of incident kinetic energy, and the surface thermal energy to the rotational energy, the mechanism of rotational excitation of CH4 scattering from Ni(111) is quantitatively unraveled. Besides rotational inelastic scattering, I report very distinct behavior of vibrationally inelastic scattering of CH4 from clean Ni(111) and Gr-Ni(111). Vibrational energy transfer to the surface dramatically changes when a clean Ni(111) surface is covered with a single layer of graphene. Theoretical calculations based upon reaction path Hamiltonian suggest that the probability of the vibrational energy transfer is related to the catalytic activity of the surface impact sites. Therefore, by monitoring the fate of the initially prepared vibrational energy, the state-to-state surface scattering technique can potentially serve as a probe of the catalytic activity of surfaces.

EPFL2022

Adsorption of low-molecular-weight molecules on the surface of a sodium smectite clay: an ab initio study

Wanda Andreoni, Pascal Clausen, Alessandro Curioni, John Christopher Plummer

We present a study of the adsorption of single molecules of volatiles, such as water, ethanol, ethyl acetate, pyridine, toluene, and n-octane, on the dry surface of a smectite clay using a series of calculations based on density functional theory. Our clay model contains both tetrahedral and octahedral substitutions, and sodium as the counterion. After establishing the accuracy of our calculations for predicting the structural features of known clays, we determine the structural features of our model clay and then characterize the changes induced by molecular adsorption and the dependence of binding on the adsorption site. In all cases, binding energies are higher in conﬁgurations bound to cations located above rings with tetrahedral substitution than for those above rings with octahedral substitutions. For molecules containing an electronegative atom, binding energies inversely correlate well with their ionization potential. Our results allow an interpretation of the trend of measured vaporization rates at low coverage and reveal that they correlate inversely with the binding energies of the molecules.

2009

Nitrogen fixation at passivated Fe nanoclusters supported by an oxide surface: Identification of viable reaction routes using density functional calculations

Harald Brune, Alfredo Pasquarello, Zeljko Sljivancanin

Using density-functional calculations, we investigate the possibility of ammonia synthesis at supported Fe nanoclusters along catalytic routes closely resembling those in biological nitrogen fixation. To achieve similar catalytic conditions as at the active site of the enzyme nitrogenase, the clusters are passivated with either S or N atoms. From calculated potential-energy profiles for the N-2 hydrogenation, we find that low-temperature synthesis of ammonia is viable at the clusters passivated by N atoms due to the strong binding energy of the N-2 molecule in the initial adsorption step.

2009

State-to-state surface scattering of methane studied by bolometric infrared laser tagging detection

Bo-Jung Chen

EPFL2022