Doubly ionized OCS bond rearrangement upon fragmentation - experiment and theory.

The dissociation of OCS2+ ions formed by photoionization of the neutral molecule at 40.81 eV is examined using threefold and fourfold electron-ion coincidence spectroscopy combined with high level quantum chemical calculations on isomeric structures and their potential energy surfaces. The dominant dissociation channel of [OCS]2+ is charge separation forming CO+ + S+ ion pairs, found here to be formed with low intensity at a lower-energy onset and with a correspondingly smaller kinetic energy release than in the more intense higher energy channel previously reported. We explain the formation of CO+ + S+ ion pairs at low as well as higher ionization energies by the existence of two predissociation channels, one involving a newly identified COS2+ metastable state. We conclude that the dominant CO+ + S+ channel with 5.2 eV kinetic energy release is reached upon OCS2+ → COS2+ isomerization, whereas the smaller kinetic energy release (of ∼4 eV) results from the direct fragmentation of OCS2+ (X3Σ-) ions. Dissociation of the COS2+ isomer also explains the existence of the minor C+ + SO+ ion pair channel. We suggest that isomerization prior to dissociation may be a widespread mechanism in dications and more generally in multiply charged ion dissociations.

Symmetry breaking in core-valence double ionisation of allene.

Conventional electron spectroscopy is an established one-electron-at-the-time method for revealing the electronic structure and dynamics of either valence or inner shell ionized systems. By combining an electron-electron coincidence technique with the use of soft X-radiation we have measured a double ionisation spectrum of the allene molecule in which one electron is removed from a C1s core orbital and one from a valence orbital, well beyond Siegbahns Electron-Spectroscopy-for-Chemical-Analysis method. This core-valence double ionisation spectrum shows the effect of symmetry breaking in an extraordinary way, when the core electron is ejected from one of the two outer carbon atoms. To explain the spectrum we present a new theoretical approach combining the benefits of a full self-consistent field approach with those of perturbation methods and multi-configurational techniques, thus establishing a powerful tool to reveal molecular orbital symmetry breaking on such an organic molecule, going beyond Löwdins standard definition of electron correlation.

Site-dependent nuclear dynamics in core-excited butadiene.

Symmetry breaking and competition between electronic decay and nuclear dynamics are major factors determining whether the memory of the initial core-hole localisation in a molecule is retained long enough to affect fragmentation. We investigate the fate of core holes localised at different sites in the free 1,3 trans butadiene molecule by using synchrotron radiation to selectively excite core electrons from different C 1s sites to π* orbitals. Fragmentation involving bonds localised at the site of the core hole provides clear evidence for preferential bond breaking for a core hole located at the terminal carbon site, while the signature of localisation is weak for a vacancy on the central carbon site. The origin of this difference is attributed to out-of-plane vibrations, and statistical evaporation of protons for vacancies located at the central carbon sites.

Abiotic molecular oxygen production-Ionic pathway from sulfur dioxide.

Molecular oxygen, O2, is vital to life on Earth and possibly also on exoplanets. Although the biogenic processes leading to its accumulation in Earth's atmosphere are well understood, its abiotic origin is still not fully established. Here, we report combined experimental and theoretical evidence for electronic state-selective production of O2 from SO2, a chemical constituent of many planetary atmospheres and one that played an important part on Earth in the Great Oxidation Event. The O2 production involves dissociative double ionization of SO2 leading to efficient formation of the [Formula: see text] ion, which can be converted to abiotic O2 by electron neutralization or by charge exchange. This formation process may contribute substantially to the abundance of O2 and related ions in planetary atmospheres, such as the Jovian moons Io, Europa, and Ganymede. We suggest that this sort of ionic pathway for the formation of abiotic O2 involving multiply charged molecular ion decomposition may also exist for other atmospheric and planetary molecules.

An experimental and theoretical characterization of the electronic structure of doubly ionised disulfur.

Using time-of-flight multiple electron and ion coincidence techniques in combination with a helium gas discharge lamp and synchrotron radiation, the double ionisation spectrum of disulfur (S[Formula: see text]) and the subsequent fragmentation dynamics of its dication are investigated. The S[Formula: see text] sample was produced by heating mercury sulfide (HgS), whose vapour at a suitably chosen temperature consists primarily of two constituents: S[Formula: see text] and atomic Hg. A multi-particle-coincidence technique is thus particularly useful for retrieving spectra of S[Formula: see text] from ionisation of the mixed vapour. The results obtained are compared with detailed calculations of the electronic structure and potential energy curves of S[Formula: see text] which are also presented. These computations are carried out using configuration interaction methodology. The experimental results are interpreted with and strongly supported by the computational results.

Single photon double and triple ionization of allene.

Double and triple ionization of allene are investigated using electron-electron, ion-ion, electron-electron-ion and electron-electron-ion-ion (ee, ii, eei, eeii) coincidence spectroscopies at selected photon energies. The results provide supporting evidence for a previously proposed roaming mechanism in H3+ formation by double ionization. The lowest vertical double ionization energy is found to be 27.9 eV, while adiabatic double ionization is not accessed by vertical ionization at the neutral geometry. The triple ionization energy is found to be close to 50 eV in agreement with theoretical predictions. The doubly charged parent ion is stable up to about 2 eV above the threshold, after which dissociations by charge separation and by double charge retention occur with comparable intensities. Fragmentation to H+ + C3H3+ starts immediately above the threshold as a slow (metastable) decay with 130.5 ± 9.9 ns mean lifetime.

Unimolecular Double Photoionization-Induced Processes in Iron Pentacarbonyl.

The dissociations of nascent Fe(CO)5++ ions created by 40.81 eV photoionization of iron pentacarbonyl have been examined using threefold and fourfold electron-ion coincidence measurements. The energies and forms of the ions have been explored by high-level calculations, revealing several new structures. The most stable form of Fe(CO)5++ has a quite different geometry from that of the neutral molecule. The dissociation pattern can be modeled as a sequence of CO evaporations followed by two-body charge separations. Each Fe(CO)n++ (n = 1-4) dication is stable in a restricted energy range; as its internal energy increases, it first ejects a neutral CO, then loses CO+ by charge separation at higher energy. In the initial stages, charge-retaining CO evaporations dominate over charge separation, but the latter become more competitive as the number of residual CO ligands decreases. At energies where ionization is mainly from the CO ligands, new Fe-C and C-C bonds are created by a mechanism which might be relevant to catalysis by Fe.

Mechanisms of site-specific photochemistry following core-shell ionization of chemically inequivalent carbon atoms in acetaldehyde (ethanal).

Site-specific fragmentation upon 1s photoionisation of acetaldehyde has been studied using synchrotron radiation and a multi-electron-ion coincidence technique based on a magnetic bottle. Experimental evidence is presented that bond rupture occurs with highest probability in the vicinity of the initial charge localisation and possible mechanisms are discussed. We find that a significant contribution to site-specific photochemistry is made by different fragmentation patterns of individual quantum states populated at identical ionisation energies.

Ultrafast Molecular Three-Electron Auger Decay.

Three-electron Auger decay is an exotic and elusive process, in which two outer-shell electrons simultaneously refill an inner-shell double vacancy with emission of a single Auger electron. Such transitions are forbidden by the many-electron selection rules, normally making their decay lifetimes orders of magnitude longer than the few-femtosecond lifetimes of normal (two-electron) Auger decay. Here we present theoretical predictions and direct experimental evidence for a few-femtosecond three-electron Auger decay of a double inner-valence-hole state in CH_{3}F. Our analysis shows that in contrast to double core holes, double inner-valence vacancies in molecules can decay exclusively by this ultrafast three-electron Auger process, and we predict that this phenomenon occurs widely.

Selectivity in fragmentation of N-methylacetamide after resonant K-shell excitation.

The fragmentation pattern of the peptide model system, N-methylacetamide, is investigated using ion time-of-flight (TOF) spectroscopy after resonant K-shell excitation. Corresponding near-edge X-ray absorption fine structure (NEXAFS) spectra recorded at high resolution at the C1s, N1s and O1s edges are presented. Analysis of the ion TOF data reveals a multitude of fragmentation channels and dissociation pathways. Comparison between the excitation of six different resonances in the vicinity of the C1s, N1s and O1s edges suggests evidence for site-selective bond breaking. In particular the breaking of the peptide bond and the N-C(α) bond show a clear correlation with resonant excitation at the N1s edge. Also, stronger tendencies towards site-selective bond breaking are found for the generation of single ions compared with ion pairs. Analysis of angular distributions of ions from breakage of the peptide bond yields a fragmentation time of <400 fs.

Versatile high-repetition-rate phase-locked chopper system for fast timing experiments in the vacuum ultraviolet and x-ray spectral region.

A novel light chopper system for fast timing experiments in the vacuum-ultraviolet (VUV) and x-ray spectral region has been developed. It can be phase-locked and synchronized with a synchrotron radiation storage ring, accommodating repetition rates in the range of ~8 to ~120 kHz by choosing different sets of apertures and subharmonics of the ring frequency (MHz range). Also the opening time of the system can be varied from some nanoseconds to several microseconds to meet the needs of a broad range of applications. Adjusting these parameters, the device can be used either for the generation of single light pulses or pulse packages from a microwave driven, continuous He gas discharge lamp or from storage rings which are otherwise often considered as quasi-continuous light sources. This chopper can be utilized for many different kinds of experiments enabling, for example, unambiguous time-of-flight (TOF) multi-electron coincidence studies of atoms and molecules excited by a single light pulse as well as time-resolved visible laser pump x-ray probe electron spectroscopy of condensed matter in the valence and core level region.

A magnetic-bottle multi-electron-ion coincidence spectrometer.

A novel multi-electron-ion coincidence spectrometer developed on the basis of a 1.5 m-long magnetic-bottle electron spectrometer is presented. Electrons are guided by an inhomogeneous magnetic field to a detector at the end of the flight tube, while a set of optics is used to extract counterpart ions to the same detector, by a pulsed inhomogeneous electric field. This setup allows ion detection with high mass resolution, without impairing the high collection efficiency for electrons. The performance of the coincidence spectrometer was tested with double ionization of carbon disulfide, CS(2) → CS(2)(2+) + e(-) + e(-), in ultrashort intense laser fields (2.8 × 10(13) W/cm(2), 280 fs, 1030 nm) to clarify the electron correlation below the rescattering threshold.

Multi-electron spectroscopy: Auger decays of the argon 2s hole.

Auger decay of an inner shell hole is an efficient way to create multiply charged ions in the gas phase. We illustrate this with the example of the argon 2s decay, and show that multi-electron coincidence spectroscopy between the 2s photoelectron and all released Auger electrons leads to a complete reconstruction of the Ar 2s decay cascade. Spectra of the intermediate and final Ar(n+) states are obtained and are compared with a theoretical model.

Application of a simple asynchronous mechanical light chopper to multielectron coincidence spectroscopy.

A simple asynchronous mechanical light chopper, based on modification of a turbo-molecular pump, has been developed to extend the interval between light pulses in single bunch operation at the Photon Factory storage ring. A pulse repetition rate of 80 kHz was achieved using a cylinder rotating at 48000 rpm, with 100 slits of 80 microm width. This allows absolute timing of particles up to 12.48 micros instead of the single-bunch period of 624 ns. We have applied the chopper together with a light pulse monitor to measure multielectron coincidence spectra using a magnetic bottle time-of-flight electron spectrometer. With such a system, the electron energies are determined without any ambiguity, the folding of coincidence spectra disappears and the effect of false coincidences is drastically reduced.

Spectroscopy and metastability of CO2 2+ molecular ions.

The spectroscopy and metastability of the carbon dioxide doubly charged ion, the CO(2) (2+) dication, have been studied with photoionization experiments: time-of-flight photoelectron photoelectron coincidence (TOF-PEPECO), threshold photoelectrons coincidence (TPEsCO), and threshold photoelectrons and ion coincidence (TPEsCO ion coincidence) spectroscopies. Vibrational structure is observed in TOF-PEPECO and TPEsCO spectra of the ground and first two excited states. The vibrational structure is dominated by the symmetric stretch except in the TPEsCO spectrum of the ground state where an antisymmetric stretch progression is observed. All three vibrational frequencies are deduced for the ground state and symmetric stretch and bending frequencies are deduced for the first two excited states. Some vibrational structure of higher electronic states is also observed. The threshold for double ionization of carbon dioxide is reported as 37.340+/-0.010 eV. The fragmentation of energy selected CO(2) (2+) ions has been investigated with TPEsCO ion coincidence spectroscopy. A band of metastable states from approximately 38.7 to approximately 41 eV above the ground state of neutral CO(2) has been observed in the experimental time window of approximately 0.1-2.3 mus with a tendency towards shorter lifetimes at higher energies. It is proposed that the metastability is due to slow spin forbidden conversion from bound excited singlet states to unbound continuum states of the triplet ground state. Another result of this investigation is the observation of CO(+)+O(+) formation in indirect dissociative double photoionization below the threshold for formation of CO(2) (2+). The threshold for CO(+)+O(+) formation is found to be 35.56+/-0.10 eV or lower, which is more than 2 eV lower than previous measurements.