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A brief overview on the status of experimental investigations into photoionization and fragmentation of fullerenes and endohedral fullerenes by absorption of a single short-wavelength photon is presented. The focus of this paper is on the endohedral Xe@C60+ molecular ion in which a xenon atom is centrally encapsulated inside a C+60 fullerene cage. Confinement resonances that result from the interference of Xe photoelectron matter waves emerging from the C+60 cavity were studied by exposing Xe@C60+ ions to synchrotron radiation of 60 to 150 eV energy which is the region of the well-known giant atomic Xe 4d excitation resonance. Photoions Xe@C n q+ (with final charge states q = 2,3,4 of the product ions and numbers of carbon atoms left in the cage) were recorded as a function of photon energy and cross sections for the individual reaction channels were determined. In addition to previous work, new final channels (q = 2; n = 60, 58 and q = 4; n = 58, 56) were observed, and thus, about 70% of the oscillator strength expected for the encapsulated Xe atom in the investigated energy range could be recovered. The present results establish the first and, so far, only conclusive experimental observation of confinement resonances in an endohedral fullerene. The data are in remarkable agreement with relativistic R-matrix calculations that accompanied the previous experimental work.

A brief overview on the status of experimental investigations into photoionization and fragmentation of fullerenes and endohedral fullerenes by absorption of a single short-wavelength photon is presented. The focus of this paper is on the endohedral Xe@C60+ molecular ion in which a xenon atom is centrally encapsulated inside a C+60 fullerene cage. Confinement resonances that result from the interference of Xe photoelectron matter waves emerging from the C+60 cavity were studied by exposing Xe@C60+ ions to synchrotron radiation of 60 to 150 eV energy which is the region of the well-known giant atomic Xe 4d excitation resonance. Photoions Xe@C n q+ (with final charge states q = 2,3,4 of the product ions and numbers of carbon atoms left in the cage) were recorded as a function of photon energy and cross sections for the individual reaction channels were determined. In addition to previous work, new final channels (q = 2; n = 60, 58 and q = 4; n = 58, 56) were observed, and thus, about 70% of the oscillator strength expected for the encapsulated Xe atom in the investigated energy range could be recovered. The present results establish the first and, so far, only conclusive experimental observation of confinement resonances in an endohedral fullerene. The data are in remarkable agreement with relativistic R-matrix calculations that accompanied the previous experimental work.

Direct double ionization of the Ar+(3p-1) ion by a single photon is investigated both experimentally and theoretically. The photon-ion merged-beams technique was employed at the Advanced Light Source in Berkeley, USA, to measure absolute cross sections in the energy range from 60 to 150 eV. In this range, three contributions to the double ionization of Ar+ are to be expected: the removal of two 3p electrons, of a 3s and a 3p electron, and of two 3s electrons. Among the possible mechanisms leading to double ionization, the TS1 (two-step one) process dominates in the near-threshold region. In TS1, a photoelectron is ejected and, on its way out, knocks out a secondary electron. This two-step mechanism is treated theoretically by multiplying the calculated cross section for direct single photoionization of a given subshell with the calculated (e,2e) ionization probability for the ejected photoelectron to knock off a secondary electron. The calculated cross section is in very good agreement with the experiment.

Experimental and theoretical cross sections are reported for single-photon single ionization of W5+ ions. Absolute measurements were conducted employing the photon-ion merged-beams technique. Detailed photon-energy scans were performed at (67 ± 10) meV resolution in the 20-160 eV range. In contrast to photoionization of tungsten ions in lower charge states, the cross section is dominated by narrow, densely-spaced resonances. Theoretical results were obtained from a Dirac-Coulomb R-matrix approach employing a basis set of 457 levels providing cross sections for photoionization of W5+ ions in the ground level as well as the and metastable excited levels. Considering the complexity of the electronic structure of tungsten ions in low charge states, the agreement between theory and experiment is satisfactory.

Photoprocesses of the endohedral fullerene ions Sc3N@C80+ and Sc3N@C80- in the gas phase have been investigated in the photon energy ranges 30-50 eV and 280-420 eV. Single and double ionization as well as single ionization accompanied by the release of a C2 dimer were observed as a function of the photon energy for the positive parent ion and double detachment was measured for the negative parent ion. The emphasis of the experiments was on the specific effects of the encapsulated trimetallic nitride cluster Sc3N on the observed reactions. Clear evidence of photoexcitation near the Sc L edge is obtained with the dominating contributions visible in the one- and two-electron-removal channels. K-vacancy production in the encapsulated central nitrogen atom is seen in the single ionization of Sc3N@C80+ but is much less pronounced in the photoionization-with-fragmentation channel. Comparison of the cross sections near the carbon K edge with the corresponding channels measured previously in the photoionization of Lu3N@C80+ reveal strong similarities. Previously predicted sharp resonance features in the ionization of Sc3N@C80+ ions below the Sc M edge are not confirmed. The experiments are accompanied by quantum-chemistry calculations in the Hartree-Fock approximation and by model calculations employing density functional theory (DFT).

In a joint experimental and theoretical endeavor, photoionization of metastable C4+(1s2sS13) ions via intermediate levels with hollow, double-K-vacancy configurations 2s2p, 2s3p, 2p3s, 2p3d, 2s4p, 2p4s, and 2p4d has been investigated. High-resolution photon-ion merged-beams measurements were carried out with the resolving power reaching up to 25 800 which is sufficient to separate the leading fine-structure components of the 2s2pP3 term. Many-body perturbation theory was employed to determine level-to-level cross sections for K-shell excitation with subsequent autoionization. The resonance energies were calculated with inclusion of electron correlation and radiative contributions. Their uncertainties are estimated to be below ±1 meV. Detailed balance confirms the present photoionization cross-section results by comparison with previous dielectronic-recombination measurements. The high accuracy of the theoretical transition energies together with the present experimental results qualify photoabsorption resonances in heliumlike ions as new, greatly improved energy-reference standards at synchrotron radiation facilities.

Single, double, and triple ionization of the C+ ion by a single photon have been investigated in the energy range 286 to 326 eV around the K-shell single-ionization threshold at an unprecedented level of detail. At energy resolutions as low as 12 meV, corresponding to a resolving power of 24 000, natural linewidths of the most prominent resonances could be determined. From the measurement of absolute cross sections, oscillator strengths, Einstein coefficients, multielectron Auger decay rates, and other transition parameters of the main K-shell excitation and decay processes are derived. The cross sections are compared to results of previous theoretical calculations. Mixed levels of agreement are found despite the relatively simple atomic structure of the C+ ion with only five electrons. This paper is a followup to a previous Letter [A. Müller, Phys. Rev. Lett. 114, 013002 (2015)PRLTAO0031-900710.1103/PhysRevLett.114.013002].

Absolute cross-section measurements are reported for single photoionization of Cn+ fullerene molecular ions (n=40, 50, 70, 76, 78, and 84) in the photon-energy range 18-70 eV. The experiments were performed by merging a mass and charge selected beam of Cn+ molecular ions with a beam of monochromatized synchrotron radiation and measuring the yield of Cn2+ product ions as a function of the photon energy. Oscillator strengths determined by integrating the measured cross sections over this energy range exhibit a linear dependence on n. The cross sections are parametrized by fits to three Lorentzian functions to represent plasmon excitations and a linear function for direct ionization. The highest-energy resonance in the data near 46 eV is similar to that previously observed in single photoionization of C60 and may be attributable to a harmonic of the dominant surface-plasmon resonance near 23 eV.

Experimental and theoretical results are reported for single-photon single ionization of the tungsten ion W4+. Absolute cross sections have been measured employing the photon-ion merged-beams setup at the Advanced Light Source in Berkeley. Detailed photon-energy scans were performed at 200 meV bandwidth in the 40-105 eV range. Theoretical results have been obtained from a Dirac-Coulomb R-matrix approach employing basis sets of 730 levels for the photoionization of W4+. Calculations were carried out for the 4f14 5s2 5p6 5d23FJ, J = 2, ground level and the associated fine-structure levels with J = 3 and 4 for the W4+ ions. In addition, cross sections have been calculated for the metastable levels 4f14 5s2 5p6 5d23P0,1,2, 1D2, 1G4, 1S0. A very satisfying agreement of theory and experiment is found for the photoionization cross section of W4+ which is remarkable given the complexity of the electronic structure of tungsten ions in low charge states.

The photon-ion merged-beams technique for the photoionisation of mass/charge selected ionised atoms, molecules and clusters by x-rays from synchrotron radiation sources is introduced. Examples for photoionisation of atomic ions are discussed by going from outer shell ionisation of simple few electron systems to inner shell ionisation of complex many electron ions. Fundamental ionisation mechanisms are elucidated and the importance of the results for applications in astrophysics and plasma physics is pointed out. Finally, the unique capabilities of the photon-ion merged-beams technique for the study of photoabsorption by nanoparticles are demonstrated by the example of endohedral fullerene ions.

Experimental and theoretical results are reported for single-photon single ionization of W2+ and W3+ tungsten ions. Experiments were performed at the photon-ion merged-beam setup of the Advanced Light Source in Berkeley. Absolute cross sections and detailed energy scans were measured over an energy range 20-90 eV at a bandwidth of 100 meV. Broad peak features with widths typically around 5 eV have been observed with almost no narrow resonances present in the investigated energy range. Theoretical results were obtained from a Dirac-Coulomb R-matrix approach. The calculations were carried out for the lowest-energy terms of the investigated tungsten ions with levels 5s 5p 5d DJ = for W2+ and 5s 5p 5d FJ= for W3+. Assuming a statistically weighted distribution of ions in the initial ground-term levels there is good agreement of theory and experiment for W3+ ions. However, for W2+ ions at higher energies there is a factor of approximately two difference between experimental and theoretical cross sections.

Cross-section measurements are reported for single and double photoionization of C60+ ions in the photon energy range 18-150 eV accompanied by the loss of zero to seven pairs of carbon atoms, as well as for fragmentation without ionization resulting in loss of two to eight pairs of C atoms in the photon energy range 18-65 eV. Absolute measurements were performed by merging a beam of C60+ molecular ions with a beam of monochromatized synchrotron radiation. Product channels involving dissociation yielding smaller fullerene fragment ions account for nearly half of the total measured oscillator strength in this energy range. The sum of cross sections for the measured product channels is compared to a published calculation of the total photoabsorption cross section of neutral C60 based on time-dependent density-functional theory. This comparison and an accounting of oscillator strengths indicate that with the exception of C58+, the most important product channels resulting from photoabsorption were accounted for in the experiment. Threshold energies for the successive removal of carbon atom pairs accompanying photoionization are also determined from the measurements.

Experimental and theoretical results are reported for photoionization of Ta-like (W+) tungsten ions. Absolute cross sections were measured in the energy range 16-245 eV employing the photon-ion merged-beam setup at the advanced light source in Berkeley. Detailed photon-energy scans at 100 meV bandwidth were performed in the 16-108 eV range. In addition, the cross section was scanned at 50 meV resolution in regions where fine resonance structures could be observed. Theoretical results were obtained from a Dirac-Coulomb R-matrix approach. Photoionization cross section calculations were performed for singly ionized atomic tungsten ions in their J = 1/2, ground level and the associated excited metastable levels with J = 3/2, 5/2, 7/2 and 9/2. Since the ion beams used in the experiments must be expected to contain long-lived excited states also from excited configurations, additional cross-section calculations were performed for the second-lowest term, J = 5/2, and for the 4F term, with J = 3/2, 5/2, 7/2 and 9/2. Given the complexity of the electronic structure of W+ the calculations reproduce the main features of the experimental cross section quite well.