Vibrationally Resolved B 1s Photoionization Cross Section of BF3.

Photoelectron diffraction is a well-established technique for structural characterization of solids, based on the interference of the native photoelectron wave with those scattered from the neighboring atoms. For isolated systems in the gas phase similar studies suffer from orders of magnitude lower signals due to the very small sample density. Here we present a detailed study of the vibrationally resolved B 1s photoionization cross section of BF3 molecule. A combination of high-resolution photoelectron spectroscopy measurements and of state-of-the-art static-exchange and time-dependent DFT calculations shows the evolution of the photon energy dependence of the cross section from a complete trapping of the photoelectron wave (low energies) to oscillations due to photoelectron diffraction phenomena. The diffraction pattern allows one to access structural information both for the ground neutral state of the molecule and for the core-ionized cation. Due to a significant change in geometry between the ground and the B 1s(-1) core-ionized state in the BF3 molecule, several vibrational final states of the cation are populated, allowing investigation of eight different relative vibrationally resolved photoionization cross sections. Effects due to recoil induced by the photoelectron emission are also discussed.

Fragmentation dynamics of doubly charged methionine in the gas phase.

The dependence of the fragmentation of doubly charged gas-phase methionine (C5H11NO2S) on the electronic-state character of the parent ion is studied experimentally by energy-resolved electron ion-ion coincidence spectroscopy. The parent dication electronic states are populated by Auger transitions following site-specific sulfur 2p core ionization. Two fragmentation channels are observed to be strongly dependent on the electronic states with vacancies in weakly bound molecular orbitals. All-electron calculations are applied to assign doubly charged final states of sulfur 2p core ionized methionine. In addition, the Car-Parrinello method is applied to model fragmentation dynamics of doubly charged methionine molecules with various initial temperatures to understand the typical characteristics of the molecular dissociation and partly to support the interpretation of experimental data.

Soft x-ray ionization induced fragmentation of glycine.

X-ray absorption commonly involves dissociative core ionization producing not only momentum correlated charged fragments but also low- and high-energy electrons capable of inducing damage in living tissue. This gives a natural motivation for studying the core ionization induced fragmentation processes in biologically important molecules such as amino acids. Here the fragmentation of amino acid glycine following carbon 1s core ionization has been studied. Using photoelectron-photoion-photoion coincidence technique, a detailed analysis on fragmentation of the sample molecule into pairs of momentum correlated cations has been carried out. The main characteristics of core ionization induced fragmentation of glycine were found to be the rupture of the C-Cα bond and the presence of the CNH(2)(+) fragment.

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.

Size selective spectroscopy of Se microclusters.

The electronic structure and photofragmentation in outer and inner valence regions of Se(n) (n ≤ 8) clusters produced by direct vacuum evaporation have been studied with size-selective photoelectron-photoion coincidence technique by using vacuum-ultraviolet synchrotron radiation. The experimental ionization potentials of these clusters were extracted from the partial ion yield measurements. The calculations for the possible geometrical structures of the Se(n) microclusters have been executed. The ionization energies of the clusters have been calculated and compared with the experimental results. In addition, theoretical fragment ion appearance energies were estimated. The dissociation energies of Se(n) clusters were derived from the recurrent relation between the gas phase enthalpies of the formation of corresponding cationic clusters and experimental ionization energies.

Fragmentation patterns of core-ionized thymine and 5-bromouracil.

Photofragmentation of thymine and 5-bromouracil into cation and neutral fragments following the core ionization by soft x-rays using photoelectron-photoion-photoion coincidence technique has been studied. The fragment ion mass spectra were recorded in coincidence with the C 1s photoelectron spectra. In the case of thymine, deuterated samples were used to identify fragments. Deuteration or bromination allowed us to study not only the main fragmentation channels of these pyrimidine bases, but also to investigate if replacement of an exocyclic functional group affects molecular fragmentation. We found that the dominant fragmentation channels involve only one starting geometry, and the base ring and other bond cleavages, leading to the detected fragments, are essentially identical between thymine and 5-bromouracil. In addition, the relative intensities of the strongest fragmentation channels were determined and compared with calculated appearance energies using ab initio unrestricted Hartree-Fock theory.

Dissociation pathways in the cysteine dication after site-selective core ionization.

A photoelectron-ion-ion coincidence experiment has been carried out on the amino acid molecule cysteine after core-ionization of the O 1s, N 1s, C 1s, and S 2p orbitals. A number of different dissociation channels have been identified. Some of them show strong site-selective dependence that can be attributed to a combination of nuclear motion in the core-ionized state and Auger processes that populate different final electronic states in the dication.

Analysis of electronic structure and its effect on magnetic properties in (001) and (110) oriented La0.7Sr0.3MnO3 thin films.

Epitaxial thin films of half-metallic oxide La0.7Sr0.3MnO3 (LSMO) have been grown in two crystalline orientations, one with the c-axis out-of-plane, the (001) orientation, and one with the c-axis in-plane, the (110) orientation. For the (110) oriented growth, there is no polar discontinuity at the substrate-film interface and hence no dead layer formation, which improves ferromagnetic interaction in the LSMO, making it highly attractive for spintronic applications. In our experiments, with x-ray diffraction, x-ray photoelectron spectroscopy and magnetic measurements, we have demonstrated that in the (110) oriented LSMO the lattice is more relaxed, leading to less deformation of electronic density around the La atom or in the MnO6 octahedra. This improved crystal and electronic structure improves the ferromagnetic properties of the films, making the Curie temperature higher by almost 15 K, which is of potential interest for spintronics. However, substrate strain induced magnetic anisotropy causes domain formation with out-of-plane components in these films, which poses some concern for practical spintronic devices.

Persistent photoinduced magnetization in the coexisting spin-glass and ferromagnetic phases of Pr0.9Ca0.1MnO3 thin film.

The persistent photoinduced magnetization (PPM) in the low bandwidth material Pr(1-x)Ca(x)MnO3 at the low hole doping level of x = 0.1 is reported. Upon zero-field cooling under photoexcitation, significant improvement of the ferromagnetic (FM) ordering was observed in the low temperature spin-glass phase. However, upon field cooling, the FM ordering was found to be suppressed due to weakening of the double-exchange interaction. High kinetic energy x-ray photoelectron spectroscopy measurements indicated a slight increase in the Mn³âº peak under photoexcitation which clarifies the weakening of the FM interaction. The fast relaxation of the PPM is discussed in view of localization of spin polarons in sites of magnetic disorders and the results are compared with previous reports of PPM in intermediate bandwidth Pr0.9Ca0.1MnO3 samples.

Resonant inelastic x-ray scattering and UV-VUV luminescence at the Be 1s edge in BeO.

We carried out a combined study of UV-VUV luminescence and resonant x-ray emission from BeO single crystals with incident photon energies in the vicinity of the Be 1s absorption edge. The x-ray emission spectra show that at the Be 1s photoabsorption edge the lattice relaxation processes in the excitation site take place already on the timescale of the radiative decay of the core excitation. Comparison of the x-ray emission and the luminescence spectra indicates that the maximum energy loss of the process of lattice relaxation during the decay of inner-shell holes is similar to the loss that occurs in the self-trapping process of valence excitons. The possible decay channels of core excitations have been discussed and the mechanism for the creation of 5.2 eV luminescence at the photoabsorption resonances has been suggested.