Double Ionization Energies Research Articles

Structure and fragmentation of doubly ionized HNCS.

Double ionization spectra of isothiocyanic acid (HNCS) have been measured using multi-electron and multi-ion coincidence techniques combined with high-level theoretical calculations. The adiabatic double ionization energy of HNCS is found at 27.1 ± 0.1eV and is associated with the formation of the X 3A″ ground state of HNCS2+. The characteristics of different dissociation channels are examined and compared to the results of electronic structure calculations obtained by systematically elongating the three bonds H-NCS, HN-CS, and HNC-S. For instance, the adiabatic double ionization energy of the NCS fragment is deduced to be 30.95 ± 0.5eV. In addition, the C+ and NS+ dissociation channels are of particular interest, possibly indicating the involvement of a structural rearrangement process upon doubly ionizing HNCS.

Double-Ionization damage to guanine nucleotide

Computations were carried out to investigate the mechanism of double-ionization damage for deoxyguanosine nucleotide. The results reveal that the polarization of the water environment reduces double-ionization energies and facilitates the hole transfer. Double ionization in solutions is independent of the counterion. The environment screens the contribution of the phosphate group. After double ionization, cleavage of the C-N glycosidic bond is a barrierless process in the gas phase. The barrier height of bond break is ∼ 4.0 kcal/mol in solutions. The C-N scission could be a potential damaged pathway. The counterion has a minor effect on the bond rupture.

Experimental and theoretical investigation of the Auger electron spectra of isothiocyanic acid, HNCS.

We investigate isothiocyanic acid, HNCS, by resonant and nonresonant Auger electron spectroscopy at the K-edge of carbon and nitrogen, and the L2,3-edge of sulfur, employing soft X-ray synchrotron radiation. The C1s and N1s ionization energies as well as the S2s and S2p ionization energies are determined and X-ray absorption spectra reveal the transitions from the core to the virtual orbitals. Final states for all normal Auger electron spectra and the resonant ones recorded at the carbon and nitrogen edge are assigned and rationalized with theoretical spectra obtained with a wave-function based protocol. The latter is based on ab initio configuration-interaction representations of the bound part of the electronic wave functions, the one-center approximation for Auger intensities, and a moment theory for band shapes. The computed spectra are in very good agreement with the experimental data and most of the relevant signals are assigned. The double ionization energy is derived from the S2p1/2 spectrum and in good agreement with a recently determined value. The Auger electron spectra are compared with those of the congener HNCO. A similar shape of the normal Auger electron spectra was found for the low binding energy final states, while intensities differed. Similarities are less pronounced in the resonant Auger electron spectra.

Search for the interatomic Auger effect in Nitrous Oxide

The interatomic Auger effect following O 1s ionization in N2O has been experimentally investigated using multi-electron coincidence spectroscopy. The expected transition energies have been established by comparison to the measured N 1s−1v−1 core-valence double ionization energies. We describe a procedure to eliminate the background of two competing processes contributing spectroscopic signatures to the same energy range, namely double Auger decay of the O 1s vacancy and direct single-photon double ionization into the N 1s−1v−1 states. While the interatomic Auger transitions could not be successfully isolated, we provide an upper boundary of the transition probability of 0.07% with respect to the dominant single Auger decay after O 1s ionization.

Electron ionisation of cyanoacetylene: ionisation cross sections and dication formation

Cyanoacetylene (HC3N) is an important trace species in the atmosphere of Titan. We report, for the first time, absolute partial electron ionisation cross sections and absolute precursor-specific partial electron ionisation cross sections for cyanoacetylene, following an experimental and computational investigation. Our methodology involves using 2D ion–ion coincidence mass spectrometry to generate relative cross sections, over the electron energy range 50–200 eV. These relative values are then normalised to an absolute scale, using a binary encounter-Bethe (BEB) calculation of the total ionisation cross section. The BEB calculation agrees well with previous determinations in the literature. The mass spectrometric observations of HC2N+ and HCN+, ions with a connectivity markedly different to that of the neutral molecule, point towards a rich cationic energy landscape possessing several local minima. Indeed, [HC3N]2+ minima involving a variety of cyclic configurations are revealed by a preliminary computational investigation, along with two minima with linear and bent geometries involving H atom migration (CCCNH2+). Determination of the energy of a transition state between these local minima indicates that the dication is able to explore the majority of this rich conformational landscape at our experimental energies. This investigation of the energetics also determines an adiabatic double ionisation energy of 30.3 eV for the lowest lying singlet state of HCCCN2+, and 30.1 eV for the lowest-lying triplet state. The bulk of the cation pairs detected in the coincidence experiment appear to originate from markedly excited dication states, not the ground state. We observe 5 two-body dissociations of HCCCN2+, and subsequent decay of one of the ions generated in such two-body processes accounts for the majority of three-body dissociations we observe.

Vacuum ultraviolet photoionization and dissociative photoionization of toluene: Experimental and theoretical insights.

The photoionization and dissociative photoionization of toluene have been studied using synchrotron radiation vacuum ultraviolet light with photon energy in the range of 8.50-25.50 eV. The ionization energies (8.82 eV) and double ionization energies (23.80 eV) of toluene as well as the appearance energies for its major fragments C7H7+ (11.17/10.71 eV), C6H5+ (13.73 eV), C5H6+ (13.58/12.50 eV), C5H5+ (16.23 eV), C4H5+ (15.64 eV), C4H4+ (16.10 eV) and C4H3+ (17.11 eV) are determined, respectively by using photoionization efficiency spectrometry. With the help of experimental and theoretical results, seven dissociative photoionization channels have been proposed: C7H7+ + H, C6H5+ + CH3, C5H6+ + C2H2, C5H5+ + C2H2 + H, C4H5+ + C3H3, C4H4+ + C3H4 and C4H3+ + C3H4 + H. In addition, the geometries of the intermediates, transition states and products involved in these photoionization and dissociative photoionization processes have been performed at the B3LYP/6-311++G(d, p) level. The mechanisms of dissociative photoionization of toluene and the intermediates and transition states involved are discussed in detail. Generally speaking, the experimental results are in agreement with theoretical calculations in this work and published literature results. Especially the mechanisms of dissociative photoionization to C4H5+, C4H4+ and C4H3+ were discussed for the first time in this work. This investigation may provide useful information on understanding the photoionization and dissociative photoionization of toluene.

A Fock space coupled cluster based probing of the single- and double-ionization profiles for the poly-cyclic aromatic hydrocarbons and conjugated polyenes.

Sequential formation of a poly-cyclic aromatic hydrocarbon (PAH) dication in the H I regions of the interstellar medium (ISM) is proposed to be a function of internal energy of the doubly ionized PAHs, which, in turn, is dependent on the single- and double-ionization potentials of the system. This sets a limit on the single- and double-ionization energies of the system(s) that can further undergo sequential absorption of two photons, leading to a dication (PAH+2). Here, we report the single-ionization (I+1) and double-ionization (I+2) energies and the I+2/I+1 ratio for some selected PAHs and conjugated polyenes obtained using the Fock space coupled cluster technique, enabling simultaneous consideration of several electronic states of different characters. The I+2 to I+1 ratio bears a constant ratio, giving allowance to determine I+2 from the knowledge of single-ionization (I+1) and vice versa. Our observations are in good agreement with the established literature findings, confirming the reliability of our estimates. The measured single- and double-ionization energies further demonstrate that the sequential formation and fragmentation of a PAH dication in the H I regions of the ISM for systems such as benzene and conjugated polyenes such as ethylene and butadiene are quite unlikely because I+2-I+1 for such system(s) is higher than the available photon energy in the H I regions of the ISM. Present findings may be useful to understand the formation and underlying decay mechanisms of multiply charged ions from PAHs and related compounds that may accentuate the exploration of the phenomenon of high-temperature superconductivity.

S2O2q+ (q = 0, 1, and 2) Molecular Systems: Characterization and Atmospheric Planetary Implications.

We use accurate ab initio methodologies at the coupled cluster level ((R)CCSD(T)) and its explicitly correlated version ((R)CCSD(T)-F12) to investigate the electronic structure, relative stability, and spectroscopy of the stable isomers of the [S2O2] system and of some of its cations and dications, with a special focus on the most relevant isomers that could be involved in terrestrial and planetary atmospheres. This work identifies several stable isomers (10 neutral, 8 cationic, and 5 dicationic), including trigonal-OSSO, cis-OSSO, and cyc-OSSO. For all these isomers, we calculated geometric parameters, fragmentation energies, and simple and double ionization energies of the neutral species. Several structures are identified for the first time, especially for the ionic species. Computations show that in addition to cis-OSSO and trans-OSSO proposed for the absorption in the near-UV spectrum of the Venusian atmosphere other S2O2, S2O2+, and S2O22+ species may contribute. Moreover, the characterization of the stability of singly and doubly charged S2O2 entities can also be used for their identification by mass spectrometry and UV spectroscopy in the laboratory or in planetary atmospheres. In sum, the quest for the main UV absorber in Venus' atmosphere is not over, since the physical chemistry of sulfur oxides in Venus' atmosphere is far from being understood.

Neutral and Multicharged Ions of Small Aluminum Oxides: Structures, Spectroscopy, and Energetics.

We use accurate ab initio methodologies at the Coupled Cluster level to compute the stable forms of AlxOyq+ (x = 1, 2; y = 1, 2; q = 0-3) species for which we derive an accurate set of geometrical and vibrational spectroscopic data. We also determine their adiabatic single, double, and triple ionization energies. These spectroscopic and thermodynamical data may help for identifying these species in laboratory, in astrophysical media, and in plasma and confirm previous observations of multi-charged AlxOy clusters by Atom Probe Tomography (ATP) coupled to mass spectrometry. They should help for identifying and understanding the complex chemical processes occurring during the Al2O3 growth in laboratory and in astrophysical media and those taking place at the degradation of Al-containing materials by high temperature corrosion/oxidation.

Hetero-site Double Core Ionization Energies with Sub-electronvolt Accuracy from Delta-Coupled-Cluster Calculations.

Benchmark scalar-relativistic delta-coupled-cluster calculations of hetero-site double core ionization energies of small molecules containing second-row elements are reported. The present study has focused on the high-spin triplet components of two-site double core-ionized states, which are single reference in character and consistent with the use of standard coupled-cluster methods. Contributions to computed double core ionization energies from electron-correlation and basis-set effects as well as corrections to the core-valence separation approximation have been analyzed. On the basis of systematic convergence of computational results with respect to these effects, delta-coupled-cluster calculations have been shown to be capable of providing accurate double core ionization energies with remaining errors estimated to be below 0.3 eV, and thus they are recommended for use to facilitate experimental studies of two-site double core-ionized states that are involved in X-ray pump/X-ray probe studies of electronic and molecular dynamics following inner shell ionization or excitation.

On the timescales of correlated electron dynamics

Recent developments yielding intense and short light pulses in the atto-second regime makes it possible to address fundamental questions on the time evolution of the electron dynamics. We demonstrate in our studies that electron pair emission from surfaces holds the promise to unravel the time scale of correlated electron dynamics. This can be achieved without atto-second light sources. We will discuss two different approaches. First we studied the Auger decay following the emission of a core-electron due to photon absorption. With coincidence spectroscopy, we demonstrate an extensive energy sharing between the Ag 4p photoelectron and the NVV Auger electron exceeding 10 eV. This result is at odds with a sequential emission of first the photoelectron and then the Auger electron. This energy width of the sharing provides access to the time scale of the emission process. We convert this to a timescale of 60 as over which the fluctuations takes place. This value is fair agreement with the theoretical calculation of the timescale to fill an exchange-correlation hole. In a second study we utilized the neutralization of ions near a surface. This is known to be efficient process and leads to electron emission via Auger-type processes. Specifically, the neutralization of He2+ ions makes available the double ionization energy. We demonstrate that the neutralization of a single He2+ ion near an Ir(100) surface leads to the emission of an electron pair. Via coincidence spectroscopy we give evidence that a sizable amount of these electron pairs originate from a correlated single step neutralization of the ion involving a total of 4 electrons from the metal. These correlated electron pairs cannot be explained in the common picture of two consecutive and independent neutralization steps. We infer a characteristic time scale for the correlated electron dynamics in the metal of 40–400 as.

Comparison of the fragmentations of phenanthrene and anthracene by low-energy electron impact

We have measured sets of mass spectra for positive ions produced by low-energy electron impact on phenanthrene. Ions have been mass resolved using a reflectron time-of-flight mass spectrometer, and the electron impact energy has been varied from 0 to 100 eV in steps of 0.5 eV. Ion yield curves of most of the fragment ions have been determined by fitting groups of adjacent peaks in the mass spectra with sequences of normalized Gaussians. The aim of this paper is to provide a detailed comparison of phenanthrene with its isomer anthracene, for which we have published results in a previous paper [1]. Appearance energies for a selection of fragment ions of phenanthrene have been determined, and are compared with anthracene. The most significant differences are observed in the ion yield curves of the ions containing 12 carbon atoms. The ion yield curves of phenanthrene have higher maximum yields and lower appearance energies compared to anthracene. For the fragments containing 9 and 10 carbon atoms the phenanthrene yields are slightly lower, but the appearance energies are the same as for anthracene. Small differences in yields are also observed for the fragments with 6 and 7 carbon atoms. The double and triple ionization energies of phenanthrene have been determined and are in agreement with anthracene.

Highly efficient double ionization of mixed alkali dimers by intermolecular Coulombic decay

As opposed to purely molecular systems where electron dynamics proceed only through intramolecular processes, weakly bound complexes such as He droplets offer an environment where local excitations can interact with neighbouring embedded molecules leading to new intermolecular relaxation mechanisms. Here, we report on a new decay mechanism leading to the double ionization of alkali dimers attached to He droplets by intermolecular energy transfer. From the electron spectra, the process is similar to the well-known shake-off mechanism observed in double Auger decay and single-photon double ionization1,2, however, in this case, the process is dominant, occurring with efficiencies equal to, or greater than, single ionization by energy transfer. Although an alkali dimer attached to a He droplet is a model case, the decay mechanism is relevant for any system where the excitation energy of one constituent exceeds the double ionization potential of another neighbouring molecule. The process is, in particular, relevant for biological systems, where radicals and slow electrons are known to cause radiation damage3. Using alkali metal dimers attached to helium droplets, a new decay mechanism for intermolecular Coulombic decay is demonstrated. The process leads to previously unresolved double ionization for excitation energies exceeding double ionization energies.

Multi reference studies of gas phase vanadium nitride di- and trications

Using ab initio configuration interaction methodologies, we compute the potentials of the doubly and triply charged vanadium nitride. By performing benchmark calculations, we show that the 4s and 3d AOs are enough for the accurate description of VN multiple ionizations. In VN2+, several deep potential wells are located below the lowest dissociation limit. Within these potential wells, long-lived rovibrational levels may be found. Specifically, we find an unconventional shape for the ground state potential of VN2+ that differs from the volcanic form typical of dications. For VN3+, four shallow potential wells were characterized that may support rovibrational levels, where metastable VN3+ can be found. Accordingly, we predict the existence of VN2+ and VN3+ species in the gas phase as already noticed experimentally for the dication VN2+. For the bound states, we provide a set of accurate spectroscopic parameters. Double and triple ionization energies of VN are computed to be 23.56 and 51.05 eV, respectively.

Valence double ionization electron spectra of CH3F, CH3Cl and CH3I

Valence double ionization electron spectra of the methyl fluoride, methyl chloride, and methyl iodide molecules have been recorded using a time-of-flight photoelectron-photoelectron coincidence technique. The spectra are interpreted by comparison with existing ionization data, Auger spectra, and theoretical calculations. The lowest double ionization energies have been found to be around 35.0eV, 30.6eV, and 26.67eV for CH3F, CH3Cl and CH3I, respectively. These energies are also compared with the predictions and implications of an empirical rule for the lowest double ionization energy in molecules.

Theoretical investigation of the long-lived metastable AlO2+ dication in gas phase

We report the results of a detailed theoretical study of the electronic ground and excited states of the gas-phase doubly charged ion AlO2+ using high-level ab initio computer calculations. Both standard and explicitly correlated methods were used to calculate their potential energy curves and spectroscopic parameters. These computations show that the ground state of AlO2+ is X2Π. The internuclear equilibrium distance of AlO2+(X2Π) is computed 1.725Å. We also deduced the adiabatic double ionization and charge stripping energies of AlO to be about 27.45eV and 17.80eV, respectively.

Theoretical characterization of vanadyl and VO3+ cations in gas phase

We investigate VO2+ and VO3+ ions theoretically. The electronic computations are performed using multi reference configuration interaction approaches in conjunction with the aug-cc-pV5Z basis set. VO2+ potential possesses a Morse-like shape instead of the common volcanic shape since both the charge retaining (V2++O) and charge separating (V++O+) dissociation channels are almost coinciding in energy. Its intense blue color is due to the A2Π–X2Δ transition. We predict VO3+ as metastable. For bound states, we derived a set of accurate spectroscopic parameters. We estimate the adiabatic double and triple ionization energies of VO to be 22.5eV and 50.9eV.

Energy differential cross sections for F9+-impact single and double ionization of He

Time-dependent close-coupling methods are used to calculate energy differential cross sections for the single and double ionization of He by impact with F9+ ions at 4.0 MeV amu−1. Single ionization energy differential cross sections using both a one active electron method and a two active electron method are compared with recent experimental results. Double ionization energy differential cross sections using a two active electron method are presented to guide future experiments.

Ab initio investigations on the CaO2+ dication

The low-lying electronic states of the CaO2+ dication are investigated using high level ab initio calculations. The electronic states converging to the first and third dissociation limits are found to be thermochemically stable, with dissociation energies ranging from 0.17eV to 0.83eV. The electronic ground state is of 3Σ- nature and the adiabatic double ionization energy of CaO is computed at 21.16eV. The main spectroscopic constants of the five low-lying bound electronic states of CaO2+ are reported. The spin–orbit coupling terms related to the X3Σ- and A3Π states are computed and used to calculate the vibronic levels of these states.

Ab initio treatment of gas phase GeO2+ doubly charged ion

Using multi reference configuration interaction methodology in connection with a large basis set, we show that GeO2+ is a metastable species either in the ground or in the electronically excited states. This confirms the observation of this dication in gas phase by mass spectrometry. In addition, we derived a set of accurate spectroscopic terms for GeO2+ bound states. At the MRCI/aug-cc-pV5Z level of theory, the adiabatic double ionization energy of GeO is computed to be ∼28.93eV.