M. Patanen

Water adsorption on TiO2 surfaces probed by soft X-ray spectroscopies: bulk materials vs. isolated nanoparticles

We describe an experimental method to probe the adsorption of water at the surface of isolated, substrate-free TiO2 nanoparticles (NPs) based on soft X-ray spectroscopy in the gas phase using synchrotron radiation. To understand the interfacial properties between water and TiO2 surface, a water shell was adsorbed at the surface of TiO2 NPs. We used two different ways to control the hydration level of the NPs: in the first scheme, initially solvated NPs were dried and in the second one, dry NPs generated thanks to a commercial aerosol generator were exposed to water vapor. XPS was used to identify the signature of the water layer shell on the surface of the free TiO2 NPs and made it possible to follow the evolution of their hydration state. The results obtained allow the establishment of a qualitative determination of isolated NPs’ surface states, as well as to unravel water adsorption mechanisms. This method appears to be a unique approach to investigate the interface between an isolated nano-object and a solvent over-layer, paving the way towards new investigation methods in heterogeneous catalysis on nanomaterials.

From double-slit interference to structural information in simple hydrocarbons

Significance Electrons emitted from equivalent centers in isolated molecules via the photoelectric effect interfere, providing an atomic-scale equivalent of the celebrated Young’s double-slit experiment. We have developed a theoretical and experimental framework to characterize such interference phenomena accurately, and we have applied it to the simplest hydrocarbons with different bond lengths and bonding types. We demonstrate that such fundamental observations can be related to crucial structural information, such as chemical bond lengths, molecular orbital composition, and quantitative assessment of many-body effects, with a very high accuracy. The experimental and theoretical tools we use are relatively simple and easily accessible, and our method can readily be extended to larger systems, including molecules of biological interest. Interferences in coherent emission of photoelectrons from two equivalent atomic centers in a molecule are the microscopic analogies of the celebrated Young’s double-slit experiment. By considering inner-valence shell ionization in the series of simple hydrocarbons C2H2, C2H4, and C2H6, we show that double-slit interference is widespread and has built-in quantitative information on geometry, orbital composition, and many-body effects. A theoretical and experimental study is presented over the photon energy range of 70–700 eV. A strong dependence of the oscillation period on the C–C distance is observed, which can be used to determine bond lengths between selected pairs of equivalent atoms with an accuracy of at least 0.01 Å. Furthermore, we show that the observed oscillations are directly informative of the nature and atomic composition of the inner-valence molecular orbitals and that observed ratios are quantitative measures of elusive many-body effects. The technique and analysis can be immediately extended to a large class of compounds.

Intramolecular photoelectron diffraction in the gas phase

We report unambiguous experimental and theoretical evidence of intramolecular photoelectron diffraction in the collective vibrational excitation that accompanies high-energy photoionization of gas-phase CF4, BF3, and CH4 from the 1s orbital of the central atom. We show that the ratios between vibrationally resolved photoionization cross sections (v-ratios) exhibit pronounced oscillations as a function of photon energy, which is the fingerprint of electron diffraction by the surrounding atomic centers. This interpretation is supported by the excellent agreement between first-principles static-exchange and time-dependent density functional theory calculations and high resolution measurements, as well as by qualitative agreement at high energies with a model in which atomic displacements are treated to first order of perturbation theory. The latter model allows us to rationalize the results for all the v-ratios in terms of a generalized v-ratio, which contains information on the structure of the above three molecules and the corresponding molecular cations. A fit of the measured v-ratios to a simple formula based on this model suggests that the method could be used to obtain structural information of both neutral and ionic molecular species.

X-ray Photoelectron Spectroscopy of Isolated Nanoparticles.

X-ray photoelectron spectroscopy (XPS) is a very efficient and still progressing surface analysis technique. However, when applied to nano-objects, this technique faces drawbacks due to interactions with the substrate and sample charging effects. We present a new experimental approach to XPS based on coupling soft X-ray synchrotron radiation with an in-vacuum beam of free nanoparticles, focused by an aerodynamic lens system. The structure of the Si/SiO2 interface was probed without any substrate interaction or charging effects for silicon nanocrystals previously oxidized in ambient air. Complete characterization of the surface was obtained. The Si 2p core level spectrum reveals a nonabrupt interface.

Charge transfer in dissociating iodomethane and fluoromethane molecules ionized by intense femtosecond X-ray pulses.

Ultrafast electron transfer in dissociating iodomethane and fluoromethane molecules was studied at the Linac Coherent Light Source free-electron laser using an ultraviolet-pump, X-ray-probe scheme. The results for both molecules are discussed with respect to the nature of their UV excitation and different chemical properties. Signatures of long-distance intramolecular charge transfer are observed for both species, and a quantitative analysis of its distance dependence in iodomethane is carried out for charge states up to I21+. The reconstructed critical distances for electron transfer are in good agreement with a classical over-the-barrier model and with an earlier experiment employing a near-infrared pump pulse.

Synchrotron‐Radiation‐Based Soft X‐Ray Electron Spectroscopy Applied to Structural and Chemical Characterization of Isolated Species, from Molecules to Nanoparticles

With its extended tunability from the IR to hard X-rays and the exceptional spectral brightness offered by the 3rd generation storage rings, synchrotron radiation (SR) is an invaluable investigation tool. Major methodological developments are now available, and are applied to simple, isolated atoms and molecules (which can be often modeled ab initio) and are then extended to the investigation of more and more complex species, up to soft and hard condensed matter. The present article highlights, with a few examples, the most recent achievements in SR-based soft X-ray electron spectroscopy applied to the structural characterization of isolated species of increasing complexity, from molecules and clusters to nanoparticles. Special attention is devoted to very high resolution studies of single molecules revealing electron diffraction and interference effects, as well as detailed information about their potential energy surfaces. These achievements are only possible based on the new opportunities offered by the most advanced SR facilities.

Site-selective photoemission from delocalized valence shells induced by molecular rotation

Due to the generally delocalized nature of molecular valence orbitals, valence-shell spectroscopies do not usually allow to specifically target a selected atom in a molecule. However, in X-ray electron spectroscopy, the photoelectron momentum is large and the recoil angular momentum transferred to the molecule is larger when the photoelectron is ejected from a light atom compared with a heavy one. This confers an extreme sensitivity of the rotational excitation to the ionization site. Here we show that, indeed, the use of high-energy photons to photoionize valence-shell electrons of hydrogen chloride offers an unexpected way to decrypt the atomic composition of the molecular orbitals due to the rotational dependence of the photoionization profiles. The analysis of the site-specific rotational envelopes allows us to disentangle the effects of the two main mechanisms of rotational excitation, based on angular momentum exchange between the molecule and either the incoming photon or the emitted electron.

Direct experimental determination of atom-molecule-solid binding energy shifts for Sb and Bi

Binding energy shifts Bi-Bi2-Bi (solid) and Sb-Sb2-Sb4-Sb (solid) have been measured for the first time directly for Bi4f and Sb4d core levels by applying synchrotron radiation excited photoelectron spectroscopy. Atomic, molecular and solid state spectra are obtained by varying the temperature of evaporated metal vapours by means of a special multichamber oven and letting the vapour condensate on a cool solid tip. Vapour and solid state spectra are created simultaneously in similar experimental conditions, making direct and accurate shift determinations possible. The effects of the multiplet fine structure of the open shell atoms are pointed out.

First in-flight synchrotron X-ray absorption and photoemission study of carbon soot nanoparticles

Many studies have been conducted on the environmental impacts of combustion generated aerosols. Due to their complex composition and morphology, their chemical reactivity is not well understood and new developments of analysis methods are needed. We report the first demonstration of in-flight X-ray based characterizations of freshly emitted soot particles, which is of paramount importance for understanding the role of one of the main anthropogenic particulate contributors to global climate change. Soot particles, produced by a burner for several air-to-fuel ratios, were injected through an aerodynamic lens, focusing them to a region where they interacted with synchrotron radiation. X-ray photoelectron spectroscopy and carbon K-edge near-edge X-ray absorption spectroscopy were performed and compared to those obtained for supported samples. A good agreement is found between these samples, although slight oxidation is observed for supported samples. Our experiments demonstrate that NEXAFS characterization of supported samples provides relevant information on soot composition, with limited effects of contamination or ageing under ambient storage conditions. The highly surface sensitive XPS experiments of airborne soot indicate that the oxidation is different at the surface as compared to the bulk probed by NEXAFS. We also report changes in soot’s work function obtained at different combustion conditions.

Vibrationally resolved C 1s photoionization cross section of CF4

The differential photoionization cross section ratio (? = 1)/(? = 0) for the symmetric stretching mode in the C 1s photoionization of CF4 was studied both theoretically and experimentally. We observed this ratio to differ from the Franck?Condon ratio and to be strongly dependent on the photon energy, even far from the photoionization threshold. The density-functional theory computations show that the ratio is significantly modulated by the diffraction of the photoelectrons by the neighbouring atoms at high photon energies. At lower energies, the interpretation of the first very strong maximum observed about 60?eV above the photoionization threshold required detailed calculations of the absolute partial cross sections, which revealed that the absolute cross section has two maxima at lower energies, which turn into one maximum in the cross section ratio because the maxima appear at slightly different energies in ? = 1 and ? = 0 cross sections. These two strong, low-energy continuum resonances originate from the trapping of the continuum wavefunction in the molecular potential of the surrounding fluorine atoms and from the outgoing electron scattering by them.