Direct Photoionization Research Articles

Temperature and Excitation Energy Dependence of the Photoionization of the F2 Center in α-Al2O3

Photoionization spectra of the F2 center in α-Al2O3 have been determined in the temperature region from 77 to 400 K by using reversible photoinduced interconversion phenomena of the F- and F2-type centers. It has been shown that photoionization of the F2 center is most effectively initiated by resonant photoexcitation of the F2 center or by excitation with a ∼4.1 eV photon. The efficiency of photoionization increases with increasing temperature, demonstrating that a thermal process is involved for the electron to be promoted from the F2-center excited states to the conduction band under the resonant (or near-resonant) excitation condition. Under excitation in the energy region higher than 4.8 eV, however, the photoionization efficiency of the F2 center is hardly dependent on temperature, indicating that the direct photoionization of the F2 center is possible in this excitation energy region. It has also been demonstrated that the temperature has a substantial effect on lowering the photoionization onset e...

A COMPREHENSIVE X-RAY ABSORPTION MODEL FOR ATOMIC OXYGEN

An analytical formula is developed to represent accurately the photoabsorption cross section of O I for all energies of interest in X-ray spectral modeling. In the vicinity of the Kedge, a Rydberg series expression is used to fit R-matrix results, including important orbital relaxation effects, that accurately predict the absorption oscillator strengths below threshold and merge consistently and continuously to the above-threshold cross section. Further minor adjustments are made to the threshold energies in order to reliably align the atomic Rydberg resonances after consideration of both experimental and observed line positions. At energies far below or above the K-edge region, the formulation is based on both outer- and inner-shell direct photoionization, including significant shake-up and shake-off processes that result in photoionization-excitation and double photoionization contributions to the total cross section. The ultimate purpose for developing a definitive model for oxygen absorption is to resolve standing discrepancies between the astronomically observed and laboratory measured line positions, and between the inferred atomic and molecular oxygen abundances in the interstellar medium from XSTAR and SPEX spectral models.

Complete double valence photoionization study of the electron spectra of krypton

Double photoionization spectra of Kr have been recorded using monochromatized synchrotron radiation of 88 eV photon energy and a versatile multielectron coincidence time-of-flight spectroscopy technique. The formation of the Kr${}^{2+}$ states of the lowest-energy configuration $4{s}^{2}4{p}^{4}$ is partly direct, producing electron pairs with a continuous distribution, and partly indirect via superexcited singly ionized states. The superexcited Kr${}^{+}$ states show strong and hitherto unexplained selectivity in branching to final Kr${}^{2+}$ states. Kr${}^{2+}$ states based on excited configurations are formed mainly by direct double photoionization.

Frustration of photoionization of Ar nanoplasma produced by extreme ultraviolet FEL pulses

We report on the laser power dependence of photoabsorptions of Ar clusters irradiated by extreme ultraviolet–free electron laser (EUV–FEL) at the wavelength of 62 nm. We measured kinetic energy distributions of fragment ions with our ion momentum spectrometer. From the measured kinetic energy distributions, we estimated charge states of irradiated Ar clusters using the classical uniformly charged sphere model. Our results show that the EUV–FEL irradiation of Ar clusters results in the frustration of direct photoionization leading to nanoplasma formation and subsequent strong electron–ion charge recombination.

Multiple ionization of neon by soft x-rays at ultrahigh intensity

At the free-electron laser FLASH, multiple ionization of neon atoms was quantitatively investigated at photon energies of 93.0 and 90.5 eV. For ion charge states up to 6+, we compare the respective absolute photoionization yields with results from a minimal model and an elaborate description including standard sequential and direct photoionization channels. Both approaches are based on rate equations and take into account a Gaussian spatial intensity distribution of the laser beam. From the comparison we conclude that photoionization up to a charge of 5+ can be described by the minimal model which we interpret as sequential photoionization assisted by electron shake-up processes. For higher charges, the experimental ionization yields systematically exceed the elaborate rate-based prediction.

Resonant Auger decay of core-excited CO molecules in intense x-ray laser pulses: the O(1s → π*) excitation

The dynamics of the resonant Auger (RA) decay of the core-excited CO*(1s−1π*) molecule in intense x-ray laser pulses is studied theoretically. The present approach includes the impact of the analogue of conical intersections of the complex potential energy surfaces of the ground and ‘dressed’ resonant states induced by intense x-ray pulses. It also takes into account the decay of the resonance and the direct photoionization of the ground state, both populating the same final ionic states coherently, as well as the direct photoionization of the resonance state itself. The individual impacts of these physical processes on the total ion yield, the CO+(A 2Π) electron spectrum and the ro-vibrational distributions of the neutral molecules remaining in the ground electronic state after the laser pulse has expired are analysed and compared to those reported previously for the C*O resonance. It is also demonstrated that the RA effect of molecules by strong laser pulses of resonant carrier frequency is an efficient process to produce two-site double-core-hole–one-particle states of CO*.

On the production of N+2 ions at the N 1s edge of the nitrogen molecule

The N+2 ion yield of the N2 molecule has been measured at the N 1s → Rydberg excitations. It displays Fano-type line shapes due to interference between direct outer-valence photoionization and participator decay of the core-excited Rydberg states. The N+2 ion yield is compared with the total intensity of the outer-valence photoelectron lines obtained recently with electron spectroscopy (Kivimäki et al 2012 Phys. Rev. A 86 012516). The increasing difference between the two curves at the higher core-to-Rydberg excitations is most likely due to soft x-ray emission processes that are followed by autoionization. The results also suggest that resonant Auger decay from the core–valence doubly excited states contributes to the N+2 ion yield at the photon energies that are located on both sides of the N 1s ionization limit.

Looking into individual coffee beans during the roasting process: direct micro-probe sampling on-line photo-ionisation mass spectrometric analysis of coffee roasting gases

A micro-probe (μ-probe) gas sampling device for on-line analysis of gases evolving in confined, small objects by single-photon ionisation time-of-flight mass spectrometry (SPI-TOFMS) was developed. The technique is applied for the first time in a feasibility study to record the formation of volatile and flavour compounds during the roasting process within (inside) or in the direct vicinity (outside) of individual coffee beans. A real-time on-line analysis of evolving volatile and semi-volatile organic compounds (VOC and SVOC) as they are formed under the mild pyrolytic conditions of the roasting process was performed. The soft-ionisation mass spectra depict a molecular ion signature, which is well corresponding with the existing knowledge of coffee roasting and evolving compounds. Additionally, thereby it is possible to discriminate between Coffea arabica (Arabica) and Coffea canephora (Robusta). The recognized differences in the roasting gas profiles reflect the differences in the precursor composition of the coffee cultivars very well. Furthermore, a well-known set of marker compounds for Arabica and Robusta, namely the lipids kahweol and cafestol (detected in their dehydrated form at m/z 296 and m/z 298, respectively) were observed. If the variation in time of different compounds is observed, distinctly different evolution behaviours were detected. Here, phenol (m/z 94) and caffeine (m/z 194) are exemplary chosen, whereas phenol shows very sharp emission peaks, caffeine do not have this highly transient behaviour. Finally, the changes of the chemical signature as a function of the roasting time, the influence of sampling position (inside, outside) and cultivar (Arabica, Robusta) is investigated by multivariate statistics (PCA). In summary, this pilot study demonstrates the high potential of the measurement technique to enhance the fundamental knowledge of the formation processes of volatile and semi-volatile flavour compounds inside the individual coffee bean.

Autoionization of Molecular Hydrogen: Where do the Fano Lineshapes Go?

Atomic autoionization following photoabsorption is a typical example of quantum interferences governed by electron-electron correlation. Coherence between direct photoionization and autoionization paths results in "Fano profiles", widely explored in atoms in the last 60 years. The advent of femto- and attosecond laser technology made time-resolved images of the delayed electron ejection in autoionization accessible, leading to the reemergence of such studies in atomic systems. The counterpart molecular phenomena show the richness, as well as the complexity, added by nuclear motion, which may proceed on similar time scales. However, Fano profiles are usually absent in measured molecular photoionization cross sections and an unequivocal parametrization of molecular autoionization signatures, similar to that introduced by Fano in atoms [U. Fano, Phys. Rev. 1961, 124, 1866] has not yet been achieved. In this work we introduce a simple semiclassical model that accounts for all the features observed in H2 photoionization and demonstrate that the interference structures observed in dissociative ionization spectra are almost exclusively due to the phase accumulated in the nuclear motion. Furthermore, we show that the temporal build-up of these structures in the energy-differential cross sections is also determined by nuclear motion. We validate our models by comparing with full-dimensional ab initio calculations solving the time-dependent Schrödinger equation.

Valence-shell single photoionization of Kr+ions: Experiment and theory

Photoionization of Kr$^+$ ions was studied in the energy range from 23.3 eV to 39.0 eV at a photon energy resolution of 7.5 meV. Absolute measurements were performed by merging beams of Kr$^+$ ions and of monochromatized synchrotron undulator radiation. Photoionization (PI) of this Br-like ion is characterized by multiple Rydberg series of autoionizing resonances superimposed on a direct photoionization continuum. Resonance features observed in the experimental spectra are spectroscopically assigned and their energies and quantum defects tabulated. The high-resolution cross-section measurements are benchmarked against state-of-the-art theoretical cross-section calculations from the Dirac-Coulomb R-matrix method.

Strong quadrupole interaction between the krypton 4p photoionization and 3d resonant excitation channels

The angular distribution of Kr 4p photoelectrons was investigated experimentally in the photon energy range of the 3d−1 → np resonant excitations. The experimental dipole and non-dipole anisotropy parameters were determined for the spin-orbit components of the Kr 4p shell. An interference effect was observed between the direct photoionization and the resonant excitation participator Auger decay processes in the photon energy dependence of the experimental anisotropy parameters.

Two-Center Resonant Photoionization

Photoionization of an atom A, in the presence of a neighboring atom B, can proceed via resonant excitation of B with subsequent energy transfer to A through two-center electron-electron correlation. We demonstrate that this two-center mechanism can strongly outperform direct photoionization at nanometer internuclear distances and possesses characteristic features in its time development and the spectrum of emitted electrons.

Quenching H2 autoionization interferences with ultrashort xuv laser pulses

In contrast with atomic photoionization or molecular direct photoionization, in the autoionization region, electron and proton kinetic-energy differential probabilities resulting from a short pulse cannot be reconstructed by the incoherent superposition of those resulting from long pulses.

Valence photoionization of the N2molecule in the region of the N1s→Rydberg excitations

The intensities of the $X$ and $A$ valence photoelectron lines of N${}_{2}$ have been found to display Fano line shapes as a function of photon energy around the N $1s\ensuremath{\rightarrow}$ Rydberg excitations. The vibrational intensity distributions of these photoelectron lines change at the N $1s\ensuremath{\rightarrow}3s\ensuremath{\sigma}$ and $3p\ensuremath{\pi}$ resonances. These effects indicate interference between direct and resonant photoionization channels. Our numerical simulations reproduce quite well the experimental results.

Two-phase jet releases, droplet dispersion and rainout, II. Rainout experiments

This paper describes the results of the first experimental stage of Phase IV of a Joint Industry Project (JIP) on liquid jets and two-phase droplet dispersion. The objective of this stage of the JIP was to generate experimental rainout data for non-flashing water and xylene experiments. See the overview companion paper I for a wider overview of the problem, model implementation and associated model validation.A range of orifice sizes (2.5 and 5 mm) and stagnation pressures (4–16 barg) were applied. Measurements included flow rate, initial droplet size, plume concentrations/temperatures for a range of downstream locations, and distributed rainout.Instead of the Phase Doppler Anemometry method used for droplet size measurements earlier in the JIP, a photographic technique was applied in an attempt to include measurement of the larger (non-spherical) droplets. This enabled a more accurate evaluation of the initial droplet size distribution and a much clearer understanding of the droplet morphology. The results showed that the droplet behaviour in the jet is more complex than had been anticipated with the mass distribution dominated by a very small number of large non-spherical droplets. Consequently a large number of spray images were required to evaluate an accurate size distribution.Distributed rainout was measured by weighing the amount of rainout in trays positioned along the jet direction. The rainout results showed a good degree of repeatability and internal consistency. They indicated that an increasing proportion of the released material did not rainout for increasing pressure. Rainout distance also increased with increasing pressure. Evaporation of the liquid was confirmed by temperature measurements, which showed the effect of evaporative cooling.Xylene concentration measurements (up to 1%) were carried out using a direct reading photoionization detector calibrated for xylene (measuring vapour only). For a limited dataset, the accuracy of these measurements was estimated by means of comparison against an alternative more time-consuming concentration method (xylene absorption onto a charcoal filter; measuring both vapour and liquid). The concentration measurements displayed several consistent qualitative features. For example, at a given downstream distance, the peak concentration increases with increasing pressure and nozzle diameter and the vertical height at which the peak is achieved increases. The cross-stream profiles displayed a consistent tendency to increased concentration at the edge of the jet, and the reason for this has not been established.Finally recommendations are provided for potential future work.

Relevance and formation mechanisms of negative ions upon ablation of Al2O3

The aim of this work is to study the significance of negative ions in the plasma produced by ablation of a simple oxide ceramic target (Al2O3) at distances and fluences typically used in pulsed-laser deposition processes. The results show that negative ions are indeed produced, the majority of which (>82%) being O− that are predominantly produced by neutralization of O+ followed by electron attachment. They represent one third of the O+ population at low fluences for a distance of 4 cm from the target at which most deposition experiments are performed. AlO− represents up to 15% of the negative ions and their amount increases at the expense of O− as fluence is increased. The most abundant as well as the fastest species in the plasma is by far Al+ that represent >80% of ions having kinetic energy <100 eV at low fluences. This result is consistent with earlier discussion on the possible existence of direct photoionization processes due to the high (6.4 eV) photon energy. Saturation effects, the formation mechanism for AlO− and Al2+, and expansion dynamics for negative ions are finally discussed.

Gas-Phase Protein Inner-Shell Spectroscopy by Coupling an Ion Trap with a Soft X-ray Beamline.

C, N, and O near-edge ion yield spectroscopy of 8+ selected electrosprayed cations of cytochrome c protein (12 kDa) has been performed by coupling a linear quadrupole ion trap with a soft X-ray beamline. The photoactivation tandem mass spectra were recorded as a function of the photon energy. Photoionization of the precursor, accompanied by CO2 loss, is the dominant relaxation process, showing high photoion stability following direct or resonant photoionization. The partial ion yields extracted from recorded mass spectra show significantly different behaviors for single and double ionization channels, which can be qualitatively explained by different Auger decay mechanisms. However, the single ionization spectra reveal characteristic structures when compared to existing near-edge X-ray absorption fine structure (NEXAFS) spectra from thin films of peptides and proteins. Therefore, the present experiment opens up new avenues for near-edge X-ray spectroscopy of macromolecules in the gas phase, overcoming the radiation damage issue or the environmental effects as due to the surface, intermolecular interactions, and solvent.

L-shell photoionization of Ar+to Ar3+ions

Absolute photoionization cross sections of Ar${}^{+}$, Ar${}^{2+}$, and Ar${}^{3+}$ ions have been measured in the 250--280 eV photon energy range. These results are compared to theoretical cross sections extracted from two new calculations we performed. They reproduce well the general behavior of the experimental spectra and the magnitude of the direct photoionization cross sections. However, the oscillator strength of the resonant structure in the spectra, dominated by $2p\ensuremath{\rightarrow}3d$ transitions, is overestimated up to 80$%$ by our calculations.

Resonant Circular Dichroism of Chiral Metal-Organic Complex

A sizable enhancement of the circular dichroism in photoelectron spectroscopy has been measured and computed for the metal complex Δ-cobalt(III) tris-acetylacetonate highest occupied molecular orbital state in the region of the Co 3p→3d Fano resonance. In the resonance the dichroism reaches the maximum value of 5% and even changes its sign as compared to the direct photoionization channel. We ascribe this enhancement to electron correlation processes, namely, with the coupling between discrete excitations and the continuum, which is correctly described in the time dependent density functional theory (TDDFT) framework. These findings open new physical aspects of photoelectron circular dichroism that now can be interpreted not only via the simple direct ionization, but also through more complex electron correlation processes.

Experimental study of linear magnetic dichroism in photoionization satellite transitions of atomic rubidium

Laser orientation in the initial state has been used to study the properties of satellite transitions in inner-shell photoionization of rubidium atoms. The linear magnetic dichroism in the angular distribution (LMDAD) has been utilized to probe the continuum waves of orbital angular momentum conserving monopole, and angular momentum changing conjugate satellites, accompanying the $4p$ ionization of atomic Rb. We show experimentally that LMDAD of both types of satellite transitions is nonzero and that LMDAD of monopole satellites, measured as a function of photon energy, mimics the LMDAD of direct photoionization, whereas the LMDAD of conjugate transitions deviates drastically from that trend. The results indicate that conjugate transitions cannot be described theoretically without explicit inclusion of electron-electron interaction. The present data can thus be used as a very precise test of current models for photoionization.