Double Ionization Threshold Research Articles

CO Dissociation Induced by 1 keV/u Ar2+ Ion

CO is one of the important molecules in dense molecular clouds, and its dissociation induced by cosmic ray heavy ions is a fundamental process for molecular breaking up and rearrangement in astronomical networks. Extensive laboratory simulations are required to understand molecular evolution in astrophysical contexts. Here, we investigate the CO dissociation induced by 1 keV/u Ar2+ using cold target recoil ion momentum spectroscopy. Kinetic energy release for double electron capture Ar2++CO→Ar0+C++O+ and transfer ionization Ar2++CO→Ar++C++O++e− was obtained. The dissociation mechanisms are attributed to different KER distributions. The autoionization process is identified below the CO2+ double ionization threshold.

Fragmentation dynamics of electron-impact double ionization of helium

We study the double ionization dynamics of a helium atom impacted by electrons with full-dimensional classical trajectory Monte Carlo simulation. The excess energy is chosen to cover a wide range of values from 5 eV to 1 keV for comparative study. At the lowest excess energy, i.e., close to the double-ionization threshold, it is found that the projectile momentum is totally transferred to the recoil-ion while the residual energy is randomly partitioned among the three outgoing electrons, which are then most probably emitted with an equilateral triangle configuration. Our results agree well with experiments as compared with early quantum-mechanical calculation as well as classical simulation based on a two-dimensional Bohr’s model. Furthermore, by mapping the final momentum vectors event by event into a Dalitz plot, we unambiguously demonstrate that the ergodicity has been reached and thus confirm a long-term scenario conceived by Wannier. The time scale for such few-body thermalization, from the initial nonequilibrium state to the final microcanonical distribution, is only about 100 attoseconds. Finally, we predict that, with the increase of the excess energy, the dominant emission configuration undergoes a transition from equilateral triangle to T-shape and finally to a co-linear mode. The associated signatures of such configuration transition in the electron-ion joint momentum spectrum and triple-electron angular distribution are also demonstrated.

Atomic autoionization in the photo-dissociation of super-excited deuterated water molecules fragmenting into D+ + O+ + D.

We present the relaxation dynamics of deuterated water molecules via autoionization, initiated by the absorption of a 61 eV photon, producing the very rare D+ + O+ + D breakup channel. We employ the COLd target recoil ion momentum spectroscopy method to measure the 3D momenta of the ionic fragments and emitted electrons from the dissociating molecule in coincidence. We interpret the results using the potential energy surfaces extracted from multi-reference configuration interaction calculations. The measured particle energy distributions can be related to a super-excited monocationic state located above the double ionization threshold of D2O. The autoionized electron energy shows a sharp distribution centered around 0.5 eV, which is a signature of the atomic oxygen autoionization occurring in the direct and sequential dissociation processes of D2O+* at a large internuclear distance. In this way, an O+ radical fragment and a low-energy electron are created, both of which can trigger secondary reactions in their environment.

Double photoionization of atomic oxygen: Feshbach resonances in the two-electron continuum

We describe a joint experimental and theoretical investigation on oxygen double photoionization—the emission of two electrons from atomic oxygen following single photon absorption. High-resolution experimental measurements were performed at the Advanced Light Source, revealing sharp resonance structure superimposed on the more familiar Wannier-like, nearly-linear background. These resonance features are attributed to ionization-plus-excitation Feshbach resonances embedded in the double ionization continuum, doubly-excited states that lie above the double-ionization threshold. Such features are absent in the double photoionization cross section of He, or other quasi-two-electron systems, for which the doubly-ionized atomic core remains inert. For a corresponding theoretical analysis, the R-matrix with pseudostates (RMPS) method was invoked by calculating final-state, two-electron resonances-plus-continua wavefunctions and corresponding single-photon absorption cross sections. Overall agreement is found in the direct, background double photoionization cross section. However, the RMPS method, using a small basis due to practical computational limitations, was unable to reproduce quantitatively the smooth background or the sharper resonance features observed in the measurements, showing instead large-scale oscillations about the experimental background, and characteristic pseudoresonance jitter, associated with an insufficient convergence of the pseudostate representation to the true two-electron infinite series of Feshbach resonances embedded in the two-electron continuum. The prominent resonance structure observed highlights the need to consider multiple excitation processes in atoms more complex than He or quasi-two-electron systems.

Quantum Theory of the Wannier Phenomenon

We employ a recently amended Born-Oppenheimer (hereafter shortly BO) approximation [1] to treat inelastic scattering of slow electrons from highly excited Rydberg atoms like e- + He(1s ns)→He-** for n ≫ 1. Along these lines we replace the standard BO set of potentials by an evolution operator. In this way we take a momentum-momentum coupling inadvertently disregarded by BO into account. The BO eigenvalue problem is now replaced by an evolution equation. One eigen-evolution has been identified as Wanner channel. That channel describes the diffraction of electron pairs from a potential ridge. That diffraction causes a phase jump of π/2 in the channel evolution. Moreover we present a new conservative attractive force controlling the motion of the electron pair as a whole in the nuclear field whose potential is given by . The coupling constant g has been calculated. That potential foreign to the standard BO approximation manifests itself by an entirely new series of isolated resonances located slightly below the double ionization threshold. This resonance ensemble compares favorably with experimental data. Further we present an evolution which forces the electron pair to the electrostatically unstable top of the potential ridge. That evolution may be regarded as quantum version of Wannier’s converging trajectory, and manifests itself here as Fresnel distribution.

Tracing intermolecular Coulombic decay of carbon-dioxide dimers and oxygen dimers after valence photoionization

We have conducted an experimental study on the photo double ionization (PDI) of carbon-dioxide dimers at photon energies of 37 and 55 eV and oxygen dimers at photon energies of 38, 41.5, and 46 eV, while focusing on the dissociation dynamics upon single-photon absorption. The investigation was performed by applying the cold-target recoil-ion momentum spectroscopy method in order to collect and record the three-dimensional momenta of the ionic fragments and emitted electrons from the dissociating dimer in coincidence. The kinetic-energy release upon fragmentation and the electron angular distributions in the laboratory and body-fixed frames, as well as the relative electron-electron emission angle, show unambiguous experimental evidence of intermolecular Coulombic decay (ICD) in carbon-dioxide dimers upon photoionization below and above the double-ionization threshold of ${\mathrm{CO}}_{2}$ monomers. The PDI of oxygen dimers is less conclusive and shows contributions from ICD and knock-off ionization mechanisms. As for atomic dimers, the present results reveal that ICD in ${\mathrm{CO}}_{2}$ dimers after valence PDI can also serve as a source for low-energy electrons, known to be very relevant in biological systems, cells, and tissues.

Rearrangement of electron shells and interchannel interaction in the K photoabsorption of Ne

A detailed theoretical analysis of the 1s photoionization of neon is presented. It is found that the most significant many-electron correlation in computing photoionization of inner shells is the rearrangement of the outer shells caused by the inner vacancy. Further noticeable effects are: (i) the polarization of the ion core by the outgoing photoelectron and (ii) the coherent effect of double excitation/ionization. The core polarization increases the photoionization cross section by about 10% at the 1s threshold, and the coherent excitation results in further increases by about 5%. Incoherent excitation of the satellite channel leads to an additional 10% increase in the photoabsorption cross section in the double-ionization threshold region.

Partial Photoionization Cross Section of Collinear eZe Helium: Numerical Confirmation of Semiclassical Predictions

Based on the semiclassical theory of chaotic scattering, Tanner et al. [J. Phys. B 40, F157 (2007)] proposed the fluctuation in the partial photoionization cross section of helium below the double-ionization threshold would show the same characteristics as in the total cross section, predicting that the Fourier spectrum of the fluctuation reveals peaks at the classical actions of closed triple collision orbits and the amplitude of the fluctuation decreases algebraically as the energy approaches the double-ionization threshold. In that paper, however, the predictions were not clearly confirmed due to the lack of experimental data with sufficient accuracy. So instead, we calculate the partial photoionization cross sections of collinear eZe helium for the energy range from the single-ionization threshold I20 to I32 in order to numerically confirm the predictions. Analysis of the fluctuation in the partial cross section shows that the predictions are indeed valid. Our findings mean that the fluctuation in the partial photoionization cross section can be described by classical triple collision orbits in the semiclassical limit. Thus it explains in a natural way the mirroring and mimicking structures observed in cross section signals for different ionization channels.

Total photoionization cross section of planar helium: scaling laws and collision orbits

The total photoionization cross section of planar helium has been calculated up to the single ionization threshold I22 of triple P states. The cross section shows chaotic fluctuations as the energy E approaches the double ionization threshold E = 0. By analyzing the fluctuating part of the cross section, we show that its amplitude decreases as for as predicted in Byun et al (2007 Phys. Rev. Lett. 98 113001). The Fourier transform of the fluctuating part reveals peaks at the classical actions of closed triple collision orbits. Furthermore, the relative height of the peaks is consistent with the semiclassical predictions. Our findings underline that the fluctuating part of the photoionization cross section can be described by classical triple collision orbits in the semiclassical limit. These orbits all lie in the collinear eZe subspace, demonstrating that the fluctuations are dominated by the dynamics of this low dimensional phase space.

Double photoionization of tribromoborazine from 25 to 138 eV

We have measured the yield for the photoproduction of singly and doubly charged parent ions of the inorganic molecule tribromoborazine [(BrBNH)${}_{3}]$, a molecule in which three bromine atoms replace three hydrogen atoms in borazine [(BH)${}_{3}$(NH)${}_{3}]$. Borazine is isoelectronic and isostructural to benzene. We compare the ratio of doubly to singly charged parent ions as a function of the photon energy to the ratio for benzene. We find similarities but also marked differences between the two molecules. The first double-ionization threshold was found to be at 28.5(4) eV.

Dissociation of cyclopropane in double ionization continuum.

Dissociative double photoionization of cyclopropane is studied in the inner-valence region using tunable synchrotron radiation. With the aid of ab initio quantum chemical calculations the energies of dication states and their favoured fragmentation pathways are determined. These are compared to the experimental appearance energies of two-body fragmentation processes and to the kinetic energy released upon dissociation. Photon energy dependent state-selective dissociation in the 25-35 eV range is found. Calculations of dissociation pathways suggest that cyclopropane ring-deformation is selectively triggered at certain photon energies. The calculations suggest that initial ring deformation essentially determines the population of different dication states that function as gateways for particular dissociation channels. The measurements show that stepwise ionization processes populate dissociative 3e'-2 states via ring-opening and Jahn-Teller active states at photon energies below the double-ionization threshold. For energies above the double-ionization threshold the kinematics indicate that double ionization takes place predominantly within the Franck-Condon region populating 3e'-1 1e''-1 states.

Bond-rearrangement and ionization mechanisms in the photo-double-ionization of simple hydrocarbons (C2H4,C2H3F, and1,1−C2H2F2) near and above threshold

We investigate bond-rearrangement driven by photo-double-ionization (PDI) near and above the double-ionization threshold in a sequence of carbon-carbon double-bonded hydrocarbon molecules: ethylene, fluoroethylene, and 1,1-difluoroethylene. We employ the kinematically complete cold target recoil ion momentum spectroscopy method to resolve all photo-double-ionization events leading to two-ion fragments. We observe changes in the branching ratios of different dissociative ionization channels depending on the presence of no, one, or two fluorine atoms. The role of the fluorine atom in the bond-rearrangement channels is intriguing, as evident by the reordering of the threshold energies of the PDI in the fluorinated molecules. These effects offer a compelling argument that the electronegativity of the fluorine (or the polarity of the molecule) strongly influences the potential energy surfaces of the molecules and drives bond rearrangement during the dissociation process. The energy sharing and the relative angle between the three-dimensional momentum vectors of the two electrons enable us to distinguish between knockout and other ionization mechanisms of the PDI processes.

Criterion for Distinguishing Sequential from Nonsequential Contributions to the Double Ionization of Helium in Ultrashort Extreme-Ultraviolet Pulses.

We quantify sequential and nonsequential contributions in two-photon double ionization of helium atoms by intense ultrashort extreme-ultraviolet pulses with central photon energies ℏω_{ctr} near the sequential double-ionization threshold. If the spectrum of such pulses overlaps both the sequential (ℏω>54.4 eV) and nonsequential (ℏω<54.4 eV) double-ionization regimes, the sequential and nonsequential double-ionization mechanisms are difficult to distinguish. By tracking the double-ionization asymmetry in joint photoelectron angular distributions, we introduce the two-electron forward-backward-emission asymmetry as a measure that allows the distinction of sequential and nonsequential contributions. Specifically, for ℏω_{ctr}=50 eV pulses with a sine-squared temporal profile, we find that the sequential double-ionization contribution is the largest at a pulse length of 650 as, due to competing temporal and spectral constraints. In addition, we validate a simple heuristic expression for the sequential double-ionization contribution in comparison with ab initio calculations.

Energy distribution of slow fragments, OH+ and O+, in water dissociation by electron impact

SynopsisIn this work, we present measurements of the energy distributions of OH+ and O+ produced in water molecule fragmentation by electron impact. We scanned the electron beam energy between 28 eV and 800 eV, examining the processes that occur from low energy transfer, below the double ionization threshold, up to processes occurring at the Oxygen K edge. The results show very different behaviors for the OH+ and O+ energy distributions for different electron energies.

Two-color above-threshold and two-photon sequential double ionization beyond the dipole approximation

Two nonlinear atomic photoprocesses are theoretically considered with the emphasis on the photoelectron angular distributions and their modifications due to violation of the dipole approximation: sequential two-photon double ionization and two-color above threshold ionization. These reactions are now accessible with X-ray free electron lasers. Both processes are exemplified by the ionization of krypton: from the 4p shell in the sequential two-photon double ionization and from the 2s shell in the two-color above-threshold ionization, which are compared to the Ar(3p) and Ne(1s) ionization, respectively. Noticeable nondipole effects are predicted.

Double photoionization in ring molecules: search of the cooper pair formation.

We provide a final state selective experimental study on the direct double photoionization of the valence states of benzene and pyrrole. The experiment is carried out using a magnetic-bottle electron time-of-flight coincidence setup at the incident photon energy region of 25-120 eV. We discuss on the recently discovered phenomenon of so-called Cooper pair formation [R. Wehlitz et al., Phys. Rev. Lett. 109, 193001 (2012)] and show that our experiment provides contradicting evidence on its existence in the proposed form. We confirm the finding of a new two-electron continuum resonance structure observed at about 30–70 eV above the double ionization threshold in benzene, provide further information from it, and suggest an alternative explanation.

Photo-double-ionization of ethylene and acetylene near threshold

We present kinematically complete measurements of the photo-double-ionization of ethylene (double CC bond) and acetylene (triple CC bond) hydrocarbons just above the double-ionization threshold. We discuss the results in terms of the coincident kinetic energy of the photoelectrons and the nuclear kinetic-energy release of the recoiling ions. We have incorporated quantum chemistry calculations to interpret which of the electronic states of the dication have been populated and trace the various subsequent fragmentation channels. We suggest pathways that involve the electronic ground and excited states of the precursor ethylene dication and explore the strong influence of the conical intersections between the different electronic states. The nondissociative ionization yield is small in ethylene and high in acetylene when compared with the dissociative ionization channels. The reason for such a striking difference is explained in part on the basis of a propensity rule that influences the population of states in the photo-double-ionization of a centrosymmetric closed-shell molecule by favoring singlet ungerade and triplet gerade final states. This propensity rule and the calculated potential-energy surfaces clarify a picture of the dynamics leading to the observed dication dissociation products.

The cage fragmentation of doubly ionized norbornane: A Born-Oppenheimer molecular dynamics study

Results are reported of Born-Oppenheimer molecular dynamics calculations performed on the singlet dication of norbornane, starting from the neutral ground state geometry. Intramolecular rearrangements and charge dissociation processes, which probably take place in the innermost valence ionization spectrum, are discussed and an analysis by means of natural bond orders and Wiberg bond indices has been performed. The outcome of these simulations and the observed cage fragmentation might explain a tremendous rise of electron-impact (e, 2e) ionization cross sections of norbornane at electron binding energies around the double-ionization threshold.

Photoionization of helium by attosecond pulses: Extraction of spectra from correlated wave functions

We investigate the photoionization spectrum of helium by attosecond XUV pulses both in the spectral region of doubly excited resonances as well as above the double ionization threshold. In order to probe for convergence, we compare three techniques to extract photoelectron spectra from the wavepacket resulting from the integration of the time-dependent Schroedinger equation in a finite-element discrete variable representation basis. These techniques are: projection on products of hydrogenic bound and continuum states, projection onto multi-channel scattering states computed in a B-spline close-coupling basis, and a technique based on exterior complex scaling (ECS) implemented in the same basis used for the time propagation. These methods allow to monitor the population of continuum states in wavepackets created with ultrashort pulses in different regimes. Applications include photo cross sections and anisotropy parameters in the spectral region of doubly excited resonances, time-resolved photoexcitation of autoionizing resonances in an attosecond pump-probe setting, and the energy and angular distribution of correlated wavepackets for two-photon double ionization.

Molecular-frame (e,2e) experiment for N2at large momentum transfer

We report molecular-frame ($e$,2$e$) cross sections for N${}_{2}$ at large momentum transfer, obtained using the electron-electron-fragment ion triple-coincidence technique. The measured angular distribution of the ($e$,2$e$) cross section for the inner-valence 2${\ensuremath{\sigma}}_{\mathrm{g}}$ orbital appears to show that the spatial character of the orbital has been directly observed in momentum space. On the other hand, experimental results for ionization to states above the double-ionization threshold suggested a larger intensity in the direction perpendicular to the molecular axis rather than parallel, an observation that our plane-wave impulse-approximation calculations fail to reproduce.