Merged-beams Technique Research Articles

Isomer-specific photofragmentation of C3H3+ at the carbon K-edge.

Individual fingerprints of different isomers of C3H3+ cations have been identified by studying photoionization, photoexcitation, and photofragmentation of C3H3+ near the carbon K-edge. The experiment was performed employing the photon-ion merged-beams technique at the photon-ion spectrometer at PETRA III (PIPE). This technique is a variant of near-edge X-ray absorption fine-structure spectroscopy, which is particularly sensitive to the 1s → π* excitation. The C3H3+ primary ions were generated by an electron cyclotron resonance ion source. C3Hn2+ product ions with n = 0, 1, 2, and 3 were observed for photon energies in the range of 279.0 eV to 295.2 eV. The experimental spectra are interpreted with the aid of theoretical calculations within the framework of time-dependent density functional theory. To this end, absorption spectra have been calculated for three different constitutional isomers of C3H3+. We find that our experimental approach offers a new possibility to study at the same time details of the electronic structure and of the geometry of molecular ions such as C3H3+.

Vibrationally Resolved Inner-Shell Photoexcitation of the Molecular Anion C2.

Carbon 1s core-hole excitation of the molecular anion C2 - has been experimentally studied at high resolution by employing the photon-ion merged-beams technique at a synchrotron light source. The experimental cross section for photo-double-detachment shows a pronounced vibrational structure associated with and core excitations of the C2 - ground level and first excited level, respectively. A detailed Franck-Condon analysis reveals a strong contraction of the C2 - molecular anion by 0.2 Å upon this core photoexcitation. The associated change of the molecule's moment of inertia leads to a noticeable rotational broadening of the observed vibrational spectral features. This broadening is accounted for in the present analysis which provides the spectroscopic parameters of the C2 - and core-excited levels.

Multiple photodetachment of oxygen anions via K -shell excitation and ionization: Direct double-detachment processes and subsequent deexcitation cascades

Experimental cross sections for m-fold photodetachment (m=2-5) of oxygen anions via K-shell excitation and ionization were measured in the photon-energy range of 525-1500 eV using the photon-ion merged-beams technique at a synchrotron light source. The measured cross sections exhibit clear signatures of direct double detachment, including double K-hole creation. The shapes of the double-detachment cross sections as a function of photon energy are in accord with Pattard's [J. Phys. B 35, L207 (2002)] empirical scaling law. We have also followed the complex deexcitation cascades that evolve subsequently to the initial double-detachment events by systematic large-scale cascade calculations. The resulting theoretical product charge-state distributions are in good agreement with the experimental findings.

Ion and neutral beams merge to measure reactions under cold interstellar medium conditions

Experiment becomes the first to employ the merged beams technique to study ion-neutral collisions at a heavy ion storage ring.

Near K-edge Photoionization and Photoabsorption of Singly, Doubly, and Triply Charged Silicon Ions

Experimental and theoretical results are presented for double, triple, and quadruple photoionization of Si+ and Si2+ ions and for double photoionization of Si3+ ions by a single photon. The experiments employed the photon–ion merged-beams technique at a synchrotron light source. The experimental photon-energy range 1835–1900 eV comprises resonances associated with the excitation of a 1s electron to higher subshells and subsequent autoionization. Energies, widths, and strengths of these resonances are extracted from high-resolution photoionization measurements, and the core-hole lifetime of K-shell ionized neutral silicon is inferred. In addition, theoretical cross sections for photoabsorption and multiple photoionization were obtained from large-scale multiconfiguration Dirac–Hartree–Fock calculations. The present calculations agree with the experiment much better than previously published theoretical results. The importance of an accurate energy calibration of laboratory data is pointed out. The present benchmark results are particularly useful for discriminating between silicon absorption in the gaseous and in the solid component (dust grains) of the interstellar medium.

Multiple photodetachment of silicon anions via K -shell excitation and ionization

Experimental cross sections for $m$-fold photodetachment ($m=3-6$) of silicon anions via $K$-shell excitation and ionization were measured in the photon-energy range of 1830-1900 eV using the photon-ion merged-beams technique at a synchrotron light source. All cross sections exhibit a threshold behavior that is masked by pre-threshold resonances associated with the excitation of a $1s$ electron to higher, either partly occupied or unoccupied atomic subshells. Results from multi-configuration Dirac-Fock (MCDF) calculations agree with the experimentally derived cross sections for photo-absorption if small energy shifts are applied to the calculated resonance positions and detachment thresholds. Moreover, a systematic approach is applied for modeling the deexcitation cascades that set in after the initial creation of a $K$-shell hole. The resulting product charge-state distributions compare well with the measured ones for direct $K$-shell detachment but less well for resonant $K$-shell excitation. The present results are potentially useful for identifying silicon anions in cold plasmas such as interstellar gas clouds.

Role of L -shell single and double core-hole production and decay in m -fold ( 1≤m≤6 ) photoionization of the Ar+ ion

Multiple ionization of the ${\mathrm{Ar}}^{+}(3{s}^{2}3{p}^{5})$ ion by a single photon has been investigated in the photon-energy range 250--1800 eV employing the photon-ion merged-beams technique. Absolute partial cross sections were measured for all ${\mathrm{Ar}}^{(1+m)+}$ product-ion channels with $1\ensuremath{\le}m\ensuremath{\le}6$ covering a size range from several tens of Mb down to a few b. Narrow $2p$-subshell excitation resonances were observed in all channels up to quadruple ionization at a photon-energy bandwidth of 52 meV. Double excitations involving a $2p$ and a $3s$ or $3p$ electron were also studied at high resolution and the measurements of the broad $2s$ excitation resonances directly showed their natural widths. Contributions of direct photo double ionization (PDI) to the production of the highest final Ar ion charge states are revealed, with PDI of the $2s$ subshell being mainly responsible for the production of ${\mathrm{Ar}}^{7+}$. The experiment made use of the PIPE setup installed at beamline P04 of the PETRA III synchrotron light source of DESY in Hamburg. The measurements were supported by theoretical calculations to identify the main contributions to the observed cross sections. Comparisons of theory and experiment show remarkable agreement but also hint to additional ionization mechanisms that are not considered in the theoretical models such as core ionization accompanied by excitations with subsequent Auger decays leading to net $m$-fold ionization with $m\ensuremath{\ge}4$.

Direct double ionization of the Ar+ M shell by a single photon

Author(s): Muller, A; Kilcoyne, ALD; Phaneuf, RA; Holste, K; Schippers, S; Kheifets, AS | Abstract: 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.

Near L-edge Single and Multiple Photoionization of Doubly Charged Iron Ions

Abstract Using the photon–ion merged-beams technique at a synchrotron light source, we have measured relative cross sections for single and up to five-fold photoionization of Fe2+ ions in the energy range of 690–920 eV. This range contains thresholds and resonances associated with ionization and excitation of 2p and 2s electrons. Calculations were performed to simulate the total absorption spectra. The theoretical results show very good agreement with the experimental data, if overall energy shifts of up to 2.5 eV are applied to the calculated resonance positions and assumptions are made about the initial experimental population of the various levels of the Fe2+([Ar]3d 6) ground configuration. Furthermore, we performed extensive calculations of the Auger cascades that result when an electron is removed from the 2p subshell of Fe2+. These computations lead to a better agreement with the measured product-charge-state distributions as compared to earlier work. We conclude that the L-shell absorption features of low-charged iron ions are useful for identifying gas-phase iron in the interstellar medium and for discriminating against the various forms of condensed-phase iron bound to composite interstellar dust grains.

Disentangling the Photodissociation Dynamics of the HF+ Molecular Radical via Kinetic-Energy-Release-Resolved F 1s Core Excitation and Ionization.

The F 1s core level photoionization of the ionic molecular radical HF+ has been studied using the photon-ion merged-beams technique at a synchrotron radiation source. Upon analyzing kinetic energy release (KER) dependent photoion yield spectra, complex ultrafast dissociation dynamics of the F 1s core hole excited σ* state can be revealed. By means of configuration-interaction electronic structure calculations of the excited molecular potential energy curves, this complex process can be attributed to a spin-dependent dissociation of the excited σ* biradical state.

Multipole-moment effects in ion-molecule reactions at low temperatures: part I - ion-dipole enhancement of the rate coefficients of the He+ + NH3 and He+ + ND3 reactions at collisional energies Ecoll/kB near 0 K.

The energy dependence of the rates of the reactions between He+ and ammonia (NY3, Y = {H,D}), forming NY2+, Y and He as well as NY+, Y2 and He, and the corresponding product branching ratios have been measured at low collision energies Ecoll between 0 and kB·40 K using a recently developed merged-beam technique [Allmendinger et al., ChemPhysChem, 2016, 17, 3596]. To avoid heating of the ions by stray electric fields, the reactions are observed within the large orbit of a highly excited Rydberg electron. A beam of He Rydberg atoms was merged with a supersonic beam of ammonia using a curved surface-electrode Rydberg–Stark deflector, which is also used for adjusting the final velocity of the He Rydberg atoms, and thus the collision energy. A collision-energy resolution of about 200 mK was reached at the lowest Ecoll values. The reaction rate coefficients exhibit a sharp increase at collision energies below ∼kB·5 K and pronounced deviations from Langevin-capture behaviour. The experimental results are interpreted in terms of an adiabatic capture model describing the rotational-state-dependent orientation of the ammonia molecules by the electric field of the He+ atom. The model faithfully describes the experimental observations and enables the identification of three classes of |JKMp〉 rotational states of the ammonia molecules showing different low-energy capture behaviour: (A) high-field-seeking states with |KM| ≥ 1 correlating to the lower component of the umbrella-motion tunnelling doublet at low fields. These states undergo a negative linear Stark shift, which leads to strongly enhanced rate coefficients; (B) high-field-seeking states subject to a quadratic Stark shift at low fields and which exhibit only weak rate enhancements; and (C) low-field-seeking states with |KM| ≥ 1. These states exhibit a positive Stark shift at low fields, which completely suppresses the reactions at low collision energies. Marked differences in the low-energy reactivity of NH3 and ND3—the rate enhancements in ND3 are more pronounced than in NH3—are quantitatively explained by the model. They result from the reduced magnitudes of the tunnelling splitting and rotational intervals in ND3 and the different occupations of the rotational levels in the supersonic beam caused by the different nuclear-spin statistical weights. Thermal capture rate constants are derived from the model for the temperature range between 0 and 10 K relevant for astrochemistry. Comparison of the calculated thermal capture rate coefficients with the absolute reaction rates measured above 27 K by Marquette et al. (Chem. Phys. Lett., 1985, 122, 431) suggests that only 40% of the close collisions are reactive.

Absolute rate coefficients for dielectronic recombination of Na-like Kr25+

The absolute rate coefficients for dielectronic recombination (DR) of sodiumlike krypton ions were measured by employing the electron-ion merged-beam technique at the heavy-ion storage ring CSRm at the Institute of Modern Physics in Lanzhou, China. The measured DR spectrum covers the electron-ion collision energy range of 0--70 eV, encompassing all of the DR resonances due to $3s\ensuremath{\rightarrow}3p$ and part of the DR resonances from $3s\ensuremath{\rightarrow}3d(\mathrm{\ensuremath{\Delta}}n=0)$ and $3s\ensuremath{\rightarrow}4l(\mathrm{\ensuremath{\Delta}}n=1)$ core excitations. A series of peaks associated with DR processes have been identified by the Rydberg formula. The experimental DR results are compared with the theoretical calculations using a relativistic configuration interaction flexible atomic code and the distorted-wave collision package autostructure. A very good agreement has been achieved between the experimental results and the theoretical calculations by considering the strong mixing among the low-energy resonances in both calculations. The experimentally derived DR spectrum is then convolved with a Maxwellian-Boltzmann distribution to obtain the temperature dependent plasma recombination rate coefficients and compared with previously available results from the literature. The present experimental result yields a precise plasma rate coefficients at the low temperature range up to $\ensuremath{\sim}1\ifmmode\times\else\texttimes\fi{}{10}^{6}\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ and the calculated data by Altun et al. [Z. Altun, A. Yumak, N. R. Badnell, S. D. Loch, and M. S. Pindzola, Astron. Astrophys. 447, 1165 (2006)] provide reliable plasma rate coefficients at high temperature range above $2\ifmmode\times\else\texttimes\fi{}{10}^{6}\phantom{\rule{0.16em}{0ex}}\mathrm{K}$.

Rate Coefficients for Dielectronic Recombination of Carbon-like 40Ca14+

Abstract Dielectronic recombination (DR) rate coefficients for carbon-like 40Ca14+ forming nitrogen-like 40Ca13+ have been measured using the electron–ion merged-beam technique at the heavy-ion storage ring CSRm at the Institute of Modern Physics in Lanzhou, China. The measured DR rate coefficients in the energy range from 0 to 92 eV cover most of the DR resonances associated with 2s 22p 2 → 2s 22p 2 and 2s 22p 2 → 2s2p 3 core transitions (ΔN = 0). Theoretical calculations of the DR cross sections were carried out by using two different state-of-the-art atomic theoretical techniques, multiconfiguration Breit–Pauli (MCBP) code AUTOSTRUCTURE and relativistic configuration interaction code FAC, to compare with the experimental rate coefficients. The theoretical calculations agree with the experimental results at collision energy higher than 10 eV. However, significant discrepancies of resonance energies and strengths can be found at collision energy below 8 eV. Temperature-dependent plasma recombination rate coefficients were derived from the measured DR rate coefficients in the energy range from 0.1 to 1000 eV and compared with the recommended atomic data from the literature. The theoretical data of Gu et al. and Zatsarinny et al. are 30% lower than the experimental results at the temperatures of photoionized plasmas, but have a very good agreement at the temperatures of collisionally ionized plasmas. Other previously published theoretical data of Jacobs et al. and Mazzotta et al. by using Burgess formula and LS-coupling calculations significantly underestimate the plasma rate coefficients in the low temperature range. The present results comprise a set of benchmark data suitable for astrophysical modeling.

Investigation of the low-energy stereodynamics in the Ne(3P2) + N2, CO reactions.

We report on an experimental investigation of the low-energy stereodynamics of the energy transfer reactions Ne(3P2) + X, producing Ne(1S) + X+ and [Ne-X]+ (X = N2 or CO). Collision energies in the range 0.2 K-700 K are obtained by using the merged beam technique. Two kinds of product ions are generated by Penning and associative ionization, respectively. The intermediate product [Ne-X]+ in vibrationally excited states can predissociate into bare ions (X+). The experimental ratio of the NeX+ and X+ product ion yields is similar for both molecules at high collision energies but diverge at collision energies below 100 K. This difference is explained by the first excited electronic state of the product ions, which is accessible in the case of CO but lies too high in energy in the case of N2.

Acceptance-angle effects on the charge transfer and energy-loss cross sections for collisions ofC4+with atomic hydrogen

The charge-transfer process for collisions of ${\mathrm{C}}^{4+}$ with atomic hydrogen is studied theoretically and experimentally in this work. Our theoretical study is based on an electron-nuclear dynamics approach applied here for the state-to-state and total contributions to the electron-capture cross sections. Our theoretical results are complemented by experimental measurements of the absolute total cross section for collisions of ${\mathrm{C}}^{4+}$ with atomic hydrogen, which were carried out using an ion-atom merged-beams technique at relative collision energies of $0.122--2.756$ keV/u and performed with an improved apparatus at Oak Ridge National Laboratory. We find that the structure observed around a collision energy of 0.5 keV/u in the experimental results is due to the combined contributions of the $3\ensuremath{\ell}$ capture cross sections, the coupling of the electronic and nuclear dynamics, and the acceptance angle in the experimental configuration. We also report the ${\mathrm{C}}^{4+}$ kinetic energy loss and stopping cross section. We find that the ${\mathrm{C}}^{4+}$ gains energy for relative collision energies between 0.1 and 10 keV/u, with a maximum at $\ensuremath{\sim}1$ keV/u. Our theoretical study shows that, to compare to the merged-beams experimental results, one has to account for effects produced by the merged path length of the apparatus.

Multiple Photodetachment of Carbon Anions via Single and Double Core-Hole Creation.

We report on new measurements of m-fold photodetachment (m=2-5) of carbon anions via K-shell excitation and ionization. The experiments were carried out employing the photon-ion merged-beams technique at a synchrotron light source. While previous measurements were restricted to double detachment (m=2) and to just the lowest-energy K-shell resonance at about 282eV, our absolute experimental m-fold detachment cross sections at photon energies of up to 1000eV exhibit a wealth of new thresholds and resonances. We tentatively identify these features with the aid of detailed atomic-structure calculations. In particular, we find unambiguous evidence for fivefold detachment via double K-hole production.

Sub-Kelvin Stereodynamics of the Ne(^{3}P_{2})+N_{2} Reaction.

We present an experimental study of the low-energy stereodynamics of the Ne(^{3}P_{2})+N_{2} reaction. Supersonic expansions of the two reactants are superposed in a merged beam experiment, where individual velocity control of the two beams allows us to reach average relative velocities of zero, yielding minimum collision energies around 60mK. We combine the merged beam technique with the orientation of the metastable neon atoms and measure the branching between two reaction channels, Penning ionization and associative ionization, as a function of neon orientation and collision energy, covering the range 0.06-700K. We find that we lose the ability to orient Ne below ≈100 K due to dynamic reorientation. Associative ionization products Ne-N_{2}^{+} predissociate with a probability of 30%-60% and that associative ionization is entirely due to reactions of the Ω=2 state, where the singly occupied p orbital of the Ne^{*} is oriented along the interatomic axis.

Photoionization of tungsten ions: experiment and theory for W5+

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.

Absolute single photoionization cross-sections of Br3+: experiment and theory

Absolute single photoionization cross section measurements for Br3+ ions are reported in the photon energy range 44.79–59.54 eV at a photon energy resolution of 21 ± 3 meV. Measurements were performed at the Advanced Light Source at Lawrence Berkeley National Laboratory using the merged-beams technique. Numerous resonance features in the experimental spectrum are assigned and their energies and quantum defect values are tabulated. The cross-section measurements are also compared with Breit–Pauli R-matrix calculations with suitable agreement over the photon energy range investigated. Analysis of the measured spectrum including Rydberg resonance series identifications produced a new emperical determination of the ionizational potential of Br3+ of 46.977 ± 0.050 eV, which is 805 meV lower than the most recently published value of 47.782 eV. This disparity between our determination and the earlier published value is similar to an 843 meV shift in the accepted ionization potential published for iso-electronic Se2+ as part of this same research program.

Dielectronic recombination rate coefficients of fluorine-like nickel

Electron-ion recombination rate coefficients for fluorine-like nickel ions have been measured by employing the merged-beam technique at the cooler storage ring CSRm at the Institute of Modern Physics in Lanzhou, China. The measured spectrum covers the energy range of 0–160 eV, including all the dielectronic recombination (DR) resonances associated with ΔN = 0 core excitations. The DR cross sections in this energy range were calculated by a relativistic configuration interaction method using the flexible atomic code (FAC). Radiative recombination (RR) cross sections were obtained from a modified version of the semi-classical Bethe & Salpeter (1957, Quantum Mechanics of One- and Two-Electron 56 Systems (Springer)) formula for hydrogenic ions. The comparison between the measurement and the calculation shows that the present theoretical model still needs to be improved at low collision energies. Temperature dependent plasma recombination rate coefficients were derived from the measured DR rate coefficients in the temperature range of 103–108 K and compared with the presently calculated result as well as previous available data in the literature. The experimentally derived data agree well with the theoretical calculations for temperatures where Ni19+ ions form in collisionally ionized plasmas. At lower temperatures typical for photo-ionized plasmas, discrepancies are found beyond the experimental uncertainty, which can be attributed to the disagreement between the measurement and the calculation of the low-lying DR resonances. The present experimental result benchmarks the plasma DR rate coefficients, in particular for temperatures below 105 K where the ΔN = 0 DR resonances dominate.