Autoionization Processes 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.

Charge-symmetric and -asymmetric fragmentation dynamics of argon dimers in slow Ar8+–Ar2 collisions

We present an experimental study of multiple-electron capture-induced fragmentation dynamics of Ar2m+ (4 ≤m≤ 7) dimer ions in 4 keV/u Ar8+–Ar2 collisions. The fragment recoil ion pairs and the charge-changing projectiles are coincidentally measured using a double coincidence technique. The branching ratios between the different charge-sharing fragmentation channels show an inherent enhancement of the asymmetric channels. The kinetic energy release (KER) distributions for the associated electron capture process show a shift in the mean KER values toward the higher side with increasing capture stabilization. The interplay between the different projectile autoionization processes sheds light on the energy depositions to the system during collisions. The Coulomb potential energy curves give a physical insight into the role of the projectile final states in the dimer fragmentation dynamics. The dimer-axis orientation-dependent cross sections for the asymmetric fragmentation channels reveal a forward–backward asymmetry that arises from the geometry of the collision system. Our findings thus give insight into the impact parameter-controlled fragmentation dynamics of multiply charged Ar2m+ dimer ions in highly charged ion–dimer slow collisions.

The Determination of Free Energy of Hydration of Water Ions from First Principles.

We model the autoionization of water by determining the free energy of hydration of the major intermediate species of water ions. We represent the smallest ions─the hydroxide ion OH-, the hydronium ion H3O+, and the Zundel ion H5O2+─by bonded models and the more extended ionic structures by strong nonbonded interactions (e.g., the Eigen H9O4+ = H3O+ + 3(H2O) and the Stoyanov H13O6+ = H5O2+ + 4(H2O)). Our models are faithful to the precise QM energies and their components to within 1% or less. Using the calculated free energies and atomization energies, we compute the pKa of pure water from first principles as a consistency check and arrive at a value within 1.3 log units of the experimental one. From these calculations, we conclude that the hydronium ion, and its hydrated state, the Eigen cation, are the dominant species in the water autoionization process.

Probing the self-ionization of liquid water with ab initio deep potential molecular dynamics.

The chemical equilibrium between self-ionized and molecular water dictates the acid-base chemistry in aqueous solutions, yet understanding the microscopic mechanisms of water self-ionization remains experimentally and computationally challenging. Herein, Density Functional Theory (DFT)-based deep neural network (DNN) potentials are combined with enhanced sampling techniques and a global acid-base collective variable to perform extensive atomistic simulations of water self-ionization for model systems of increasing size. The explicit inclusion of long-range electrostatic interactions in the DNN potential is found to be crucial to accurately reproduce the DFT free energy profile of solvated water ion pairs in small (64 and 128 H2O) cells. The reversible work to separate the hydroxide and hydronium to a distance [Formula: see text] is found to converge for simulation cells containing more than 500 H2O, and a distance of [Formula: see text] 8 Å is the threshold beyond which the work to further separate the two ions becomes approximately zero. The slow convergence of the potential of mean force with system size is related to a restructuring of water and an increase of the local order around the water ions. Calculation of the dissociation equilibrium constant illustrates the key role of long-range electrostatics and entropic effects in the water autoionization process.

HORTENSIA, a program package for the simulation of nonadiabatic autoionization dynamics in molecules.

We present a program package for the simulation of ultrafast vibration-induced autoionization dynamics in molecular anions in the manifold of the adiabatic anionic states and the discretized ionization continuum. This program, called HORTENSIA (Hopping Real-time Trajectories for Electron-ejection by Nonadiabatic Self-Ionization in Anions), is based on the nonadiabatic surface-hopping methodology, wherein nuclei are propagated as an ensemble along classical trajectories in the quantum-mechanical potential created by the electronic density of the molecular system. The electronic Schrödinger equation is numerically integrated along the trajectory, providing the time evolution of electronic state coefficients, from which switching probabilities into discrete electronic states are determined. In the case of a discretized continuum state, this hopping event is interpreted as the ejection on an electron. The derived diabatic and nonadiabatic couplings in the time-dependent electronic Schrödinger equation are calculated from anionic and neutral wavefunctions obtained from quantum-chemical calculations with commercially available program packages interfaced with our program. Based on this methodology, we demonstrate the simulation of autoionization electron kinetic energy spectra that are both time- and angle-resolved. In addition, the program yields data that can be interpreted easily with respect to geometric characteristics, such as bonding distances and angles, which facilitate the detection of molecular configurations important for the autoionization process. Furthermore, several useful extensions are included, namely, tools for the generation of initial conditions and input files as well as for the evaluation of output files, all of this both through console commands and a graphical user interface.

Effect of charge and solvation shell on non-radiative decay processes in s-block cationic metal ion water clusters.

Intermolecular Coulombic decay or electron transfer-mediated decay are the autoionization processes through which a molecule can relax. This relaxation is only possible if the inner valence's ionization potential (IP) exceeds the system's double ionization potential (DIP). To study the effects of charge and solvation shell, we have calculated the IP, DIP values, and lifetime of Na-2s and Mg-2s temporary bound states in various optimized structures of Na+-(H2O)n and Mg2+-(H2O)n (n = 1-5) micro-solvated clusters, where n water molecules are distributed in a way that some are directly bound to the metal ion and the rest to the water molecules. The first and second solvation shells are the names for the former and the latter water-binding positions, respectively. For a given n, the lifetime of decaying states is longer when water molecules are in the second solvation shell. We found that the Mg-2p state can decay for all n values in Mg2+-(H2O)n clusters, whereas the Na-2p state's decay is possible for n ≥ 2 in Na+-(H2O)n clusters. Our findings highlight the influence of metal ions' charge, different solvation shell structures, and the number of water molecules on the decay rate. These systems are relevant to the human body, which makes this study significant.

Dynamics of the H2 levels lying between the third and fourth dissociation thresholds (132 500 – 139 000 cm− 1)

The absorption spectrum of H2 at room temperature, was recorded at high resolution at the BESSY II synchrotron radiation storage ring in the 132500 – 139000 cm−1 energy range, allowing the study of the dynamics of the excited levels (npσ 1Σu+ and npπ 1Πu±) located between the H(n = 3) + H(n = 1) and H(n = 4) + H(n = 1) thresholds. Ionization anddissociation were found to compete for levels with n ≤ 8. In most cases, for the levels with n > 8, ionization is the only decay channel. The relative importance of the direct ionization, direct dissociation, autoionization and predissociation processes was evaluated for the whole energy range. From the different detected channels, and from the comparison with theoretical approaches, the main continua responsible for the predissociations were assigned to the V and to the B"B¯ states and the H(3p)/H(n = 3) ratios of the dissociation fragments from the 4pπ and 5pπ 1Πu- levels were measured. Molecular fluorescence was observed for few 1Πu- levels and the importance of its contribution is discussed.

Measuring autoionization decay lifetimes of optically forbidden inner valence excited states in neon atoms with attosecond noncollinear four-wave-mixing spectroscopy

Attosecond noncollinear four wave mixing spectroscopy with one attosecond extreme ultraviolet (XUV) pulse and two few-cycle near-infrared (NIR) pulses was used to measure the autoionization decay lifetimes of inner valence electronic excitations in neon atoms. After a 43-48 eV XUV photon excites a 2s electron into the 2s2p6[np] Rydberg series, broadband NIR pulses couple the 2s2p6[3p] XUV-bright state to neighboring 2s2p6[3s] and 2s2p6[3d] XUV-dark states. Controllable delays of one or both NIR pulses with respect to the attosecond XUV pulse reveal the temporal evolution of either the dark or bright states, respectively. Experimental lifetimes for the 3s, 3p, and 3d states are measured to be 7 +/- 2 fs, 48 +/- 8 fs, and 427 +/- 40 fs, respectively, with 95% confidence. Accompanying calculations with two independent ab initio theoretical methods, NewStock and ASTRA, verify the findings. The results support the expected trend that the autoionization lifetime should be longer for states that have a smaller penetration in the radial region of the 2s core hole, which in this case is for the higher angular momentum Rydberg orbitals. The underlying theory thus links the lifetime results to electron correlation and provides an assessment of the direct and exchange terms in the autoionization process.

Quantum-classical dynamics of vibration-induced autoionization in molecules.

We present a novel method for the simulation of the vibration-induced autoionization dynamics in molecular anions in the framework of the quantum-classical surface hopping approach. Classical trajectories starting from quantum initial conditions are propagated on a quantum-mechanical potential energy surface while allowing for autoionization through transitions into discretized continuum states. These transitions are induced by the couplings between the electronic states of the bound anionic system and the electron-detached system composed of the neutral molecule and the free electron. A discretization scheme for the detached system is introduced, and a set of formulas is derived that enable the approximate calculation of couplings between the bound and free-electron states. We demonstrate our method on the example of the anion of vinylidene, a high-energy isomer of acetylene, for which detailed experimental data are available. Our results provide information on the time scale of the autoionization process and give insight into the energetic and angular distribution of the ejected electrons, as well as the associated changes in the molecular geometry. We identify the formation of structures with reduced C-C bond lengths and T-like conformations through bending of the CH2 group with respect to the C-C axis and point out the role of autoionization as a driving process for the isomerization to acetylene.

Unravelling the electronic structure of the silicon dimer using threshold photoelectron spectroscopy

The low-lying electronic states of silicon dimer (Si) and its cation (Si) have been studied by single-photon photoelectron spectroscopy combining a flow-tube reactor, vacuum-ultraviolet synchrotron radiation, and a double imaging photoelectron/photoion spectrometer. The energy range covered in this study (7.0−9.5 eV) allowed to observe several photoionising transitions involving the three lowest electronic states of Si (, , ) and five of the six lowest states of Si (, , , , and ). Using ab initio calculations and Franck-Condon simulations, several electronic transitions are identified which bring new elements in the description of the dense electronic landscapes of the silicon dimer and its cation. Interestingly, one of the most intense transitions is spin-forbidden () and is most probably observed through autoionisation processes by spin interactions.

Autoionization of Ultracold Cesium Rydberg Atom in 37D5/2 State

We present the observation of an autoionization of cesium 37D5/2 Rydberg atoms in ultracold gases and analyze the autoionization mechanism. The autoionization process is investigated by varying the delay time tD and Rydberg atomic density. The dependence of ionization signals on Rydberg density shows that the Rydberg density has an effect on not only the initial ion signals but also the evolution of the Rydberg atoms. The results reveal that the initial ionization of 37D5/2 Rydberg atoms is mostly attributed to the blackbody radiation (BBR)-induced photoionization, and the BBR-induced transitions to the nearby Rydberg states that lead to further ionization. Our work plays a significant role in investigating the collision between Rydberg atoms and many-body physics.

Pulsed-ramped-field-ionization zero-kinetic-energy photoelectron spectroscopy: a methodological advance.

A new experimental method has been developed to record photoelectron spectra based on the well-established pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopy technique and inspired by the data treatment employed in slow photoelectron spectroscopy. This method has been successfully applied to two well-known systems: the X+2Πg,1/2(v+ = 0) ← X1Σ+g(v = 0) and the X+1Σ+(v+ = 2) ← X2Π1/2(v = 0) ionizing transitions of CO2 and NO, respectively. The first results highlight several advantages of our technique such as an improved signal-to-noise ratio without degrading the spectral resolution and a direct field-free energy determination. The data obtained for NO indicate that this method might be useful for studying field-induced autoionization processes.

High resolution threshold photoelectron spectrum and autoionization processes of S2 up to 15.0 eV

VUV photoionization dynamics of the S2 molecule were re-investigated from threshold up to 15.0 eV, using synchrotron radiation coupled with double imaging photoelectron/photoion coincidence featuring high resolution capabilities. We measured the first threshold photoelectron spectrum of S2 achieving higher resolution than previous literature to derive accurate spectroscopic constants for a few electronic states of the cation including the X2ΠΩ,g ground state and the a4Πu, b4Σg–, and B2Σg– states. We also recorded the total ion yield for S2 up to a photon energy of 15.0 eV which, combined with the threshold photoelectron spectrum, led to the assignment of various autoionizing Rydberg series.

Auger decay in dispersing and absorbing environments

We develop a quantum-optical description of Auger decay, which is an ultrafast, high-energy autoionization process, on the basis of macroscopic quantum electrodynamics. One consequence of this perspective is a simple analytical formula for the free-space Auger rate which we compare with available rates of the F-like isoelectronic sequence. More importantly, the formalism enables us to study the Auger decay in different dispersing and absorbing environments. We show that in contrast to common assumptions the Auger rate can be influenced by an environment, presenting two simple examples, namely a dielectric surface and a surrounding bulk medium.

The Resonant and Normal Auger Spectra of Ozone

In this work, we outline a general method for calculating Auger spectra in molecules, which accounts for the underlying symmetry of the system. This theory starts from Fano’s formulation of the interaction between discrete and continuum states, and it generalizes this formalism to deal with the simultaneous presence of several intermediate quasi-bound states and several non-interacting decay channels. Our theoretical description is specifically tailored to resonant autoionization and Auger processes, and it explicitly includes the incoming wave boundary conditions for the continuum states and an accurate treatment of the Coulomb repulsion. This approach is implemented and applied to the calculation of the K−LL Auger and autoionization spectra of ozone, which is a C2v symmetric molecule, whose importance in our atmosphere to filter out radiation has been widely confirmed. We also show the effect that the molecular point group and, in particular, the localization of the core-hole in the oxygen atoms related by symmetry operations, has on the electronic structure of the Auger states and on the spectral lineshape by comparing our results with the experimental data.

Feshbach–Fano approach for calculation of Auger decay rates using equation-of-motion coupled-cluster wave functions. I. Theory and implementation

X-ray absorption creates electron vacancies in the core shell. These highly excited states often relax by Auger decay-an autoionization process in which one valence electron fills the core hole and another valence electron is ejected into the ionization continuum. Despite the important role of Auger processes in many experimental settings, their first-principles modeling is challenging, even for small systems. The difficulty stems from the need to describe many-electron continuum (unbound) states, which cannot be tackled with standard quantum-chemistry methods. We present a novel approach to calculate Auger decay rates by combining Feshbach-Fano resonance theory with the equation-of-motion coupled-cluster single double (EOM-CCSD) framework. We use the core-valence separation scheme to define projectors into the bound (square-integrable) and unbound (continuum) subspaces of the full function space. The continuum many-body decay states are represented by products of an appropriate EOM-CCSD state and a free-electron state, described by a continuum orbital. The Auger rates are expressed in terms of reduced quantities, two-body Dyson amplitudes (objects analogous to the two-particle transition density matrix), contracted with two-electron bound-continuum integrals. Here, we consider two approximate treatments of the free electron: a plane wave and a Coulomb wave with an effective charge, which allow us to evaluate all requisite integrals analytically; however, the theory can be extended to incorporate a more sophisticated description of the continuum orbital.

Dissociation of High-Lying Electronic States of NO2+ in the 15.5-20 eV Region.

We present a dissociative photoionization study of NO2 in the 15.5-20 eV energy range using synchrotron radiation-based double imaging photoelectron photoion coincidence (i2PEPICO) spectroscopy. The high-lying electronic states of the NO2+ cation, c 3B1, C 1B1, d 3A1, e 3B2, and D 1B2, are prepared in well-resolved vibronic states in order to study their individual dissociation mechanisms. Up to eight dissociation limits of NO2+ are reached, and mass-selected threshold photoelectron spectra (TPES) show that the c 3B1, C 1B1, and d 3A1 states predominantly dissociate into the NO+ + O products, while the e 3B2 and D 1B2 states can undergo fragmentation into both the NO+ + O and the O+ + NO channels, as well as the O2+ + N channel with a small yield. Overall, these product yields are found to be quite sensitive to autoionization processes. Mass-selected high-resolution electron and ion kinetic energy correlation diagrams reveal dissociative mechanisms that possess strong state-specific character.

Coupled nuclear-electronic decay dynamics of O2 inner valence excited states revealed by attosecond XUV wave-mixing spectroscopy.

Multiple Rydberg series converging to the O2+c4Σ-u state, accessed by 20-25 eV extreme ultraviolet (XUV) light, serve as important model systems for the competition between nuclear dissociation and electronic autoionization. The dynamics of the lowest member of these series, the 3sσg state around 21 eV, has been challenging to study owing to its ultra-short lifetime (<10 fs). Here, we apply transient wave-mixing spectroscopy with an attosecond XUV pulse to investigate the decay dynamics of this electronic state. Lifetimes of 5.8 ± 0.5 fs and 4.5 ± 0.7 fs at 95% confidence intervals are obtained for v = 0 and v = 1 vibrational levels of the 3s Rydberg state, respectively. A theoretical treatment of predissociation and electronic autoionization finds that these lifetimes are dominated by electronic autoionization. The strong dependence of the electronic autoionization rate on the internuclear distance because of two ionic decay channels that cross the 3s Rydberg state results in the different lifetimes of the two vibrational levels. The calculated lifetimes are highly sensitive to the location of the 3s potential with respect to the decay channels; by slight adjustment of the location, values of 6.2 and 5.0 fs are obtained computationally for the v = 0 and v = 1 levels, respectively, in good agreement with experiment. Overall, an intriguing picture of the coupled nuclear-electronic dynamics is revealed by attosecond XUV wave-mixing spectroscopy, indicating that the decay dynamics are not a simple competition between isolated autoionization and predissociation processes.

Autoionization and Dressing of Excited Excitons by Free Carriers in Monolayer WSe_{2}.

We experimentally demonstrate dressing of the excited exciton states by a continuously tunable Fermi sea of free charge carriers in a monolayer semiconductor. It represents an unusual scenario of two-particle excitations of charged excitons previously inaccessible in conventional material systems. We identify excited state trions, accurately determine their binding energies in the zero-density limit for both electron- and hole-doped regimes, and observe emerging many-body phenomena at elevated doping. Combining experiment and theory we gain access to the intra-exciton coupling facilitated by the interaction with free charge carriers. We provide evidence for a process of autoionization for quasiparticles, a unique scattering pathway available for excited states in atomic systems. Finally, we demonstrate a complete transfer of the optical transition strength from the excited excitons to dressed Fermi-polaron states as well as the associated light emission from their nonequilibrium populations.

Contribution of Autoionization Processes to the Electronic Stopping Power

It is shown that the excitation of autoionization states during the collisions of keV-energy ions with a solid plays a determining role in the formation of inelastic energy losses and, accordingly, the electronic-stopping cross section Se. It is proposed to estimate the Se values using the relationship between the cross section for autoionization-state excitation and the ionization cross section. For cases where the ionization cross sections are unknown, scaling is used to calculate the ionization cross sections when the L and M shells are excited. The threshold dependence of Se versus the energy of bombarding ions is predicted.