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Dynamical response of water exposed to x-rays is of utmost importance in a wealth of science areas. We exposed isolated water isotopologues to short x-ray pulses from a free-electron laser and detected momenta of all produced ions in coincidence. By combining experimental results and theoretical modeling, we identify significant structural dynamics with characteristic isotope effects in H2O2+, D2O2+, and HDO2+, such as asymmetric bond elongation and bond-angle opening, leading to two-body or three-body fragmentation on a timescale of a few femtoseconds. A method to disentangle the sequences of events taking place upon the consecutive absorption of two x-ray photons is described. The obtained deep look into structural properties and dynamics of dissociating water isotopologues provides essential insights into the underlying mechanisms. [ABSTRACT FROM AUTHOR]

Momentum vector correlation is a powerful tool to study molecular dissociation. We have studied the three-body fragmentation of carbon disulfide after sulfur 1s photoionization by means of momentum imaging techniques. Concerted and sequential pathways are disentangled in three-body fragmentation using adapted analysis strategies. In particular, we introduce various data visualization schemes that are proved to be particularly efficient to determine dissociation dynamics. [ABSTRACT FROM AUTHOR]

Spectra reflecting the formation of single-site double-core-hole pre-edge states involving the N 1s and C 1s core levels of acetonitrile have been recorded by means of high-resolution single-channel photoelectron spectroscopy using hard X-ray excitation. The data are interpreted with the aid of ab initio quantum chemical calculations, which take into account the direct or conjugate nature of this type of electronic states. Furthermore, the photoelectron spectra of N 1s and C 1s singly core-ionized states have been measured. From these spectra, the chemical shift between the two C 1s−1 states is estimated. Finally, by utilizing C 1s single and double core-ionization potentials, initial and final state effects for the two inequivalent carbon atoms have been investigated. [ABSTRACT FROM AUTHOR]

Resonant Auger electron spectroscopic study at the symmetry-forbidden 1 a 1 g → 6 a 1 g excitation below the S K -shell threshold of SF 6 is reported. Partial electron yield and resonant K L L Auger spectra have been measured by using monochromatized undulator synchrotron radiation. By changing the photon energy in small steps, a so-called 2D map is produced. In this map, the dipole-forbidden transition exhibits spectral features (e.g., an S-shaped dispersion relation), which are well known and understood for dipole-allowed transitions. We validate by a theory that for the case of dipole-forbidden transitions, these spectral features can be analyzed in the same way as previously established for the dipole-allowed ones. This approach grants information on the nuclear dynamics in the K -shell core-excited states of SF 6 on the femtosecond (fs) timescale. In particular, for the potential-energy curves of the states S 1 s − 1 6 a 1 g and S 2 p − 2 6 a 1 g , the slopes at the equilibrium distance of the ground state are derived. Symmetry breaking as a result of ultrafast vibronic coupling is revealed by the population of the electronically forbidden excited state. [ABSTRACT FROM AUTHOR]

Auger decay after photoexcitation or photoemission of an electron from a deep inner shell in the hard X-ray regime can be rather complex, implying a multitude of phenomena such as multiple-step cascades, post-collision interaction (PCI), and electronic state-lifetime interference. Furthermore, in a molecule nuclear motion can also be triggered. Here we discuss a comprehensive theoretical method which allows us to analyze in great detail Auger spectra measured around an inner-shell ionization threshold. HCl photoexcited or photoionized around the deep Cl 1s threshold is chosen as a showcase. Our method allows calculating Auger cross sections considering the nature of the ground, intermediate and final states (bound or dissociative), and the evolution of the relaxation process, including both electron and nuclear dynamics. In particular, we show that we can understand and reproduce a so-called experimental 2D-map, consisting of a series of resonant Auger spectra measured at different photon energies, therefore obtaining a detailed picture of all above-mentioned dynamical phenomena at once. [ABSTRACT FROM AUTHOR]

Doppler and recoil effects are an integral part of the photoemission process at the high kinetic energies reached in hard x-ray photo-electron spectroscopy (HAXPES) and have a major effect on the observed lineshape, resulting in broadening, energy losses and discrete excitations. These effects can be modeled with a high degree of detail for small systems like diatomic molecules, for larger systems such treatment is often superfluous as the fine spectral features are not observable. We present a united description of the Doppler and recoil effects for arbitrary polyatomic systems and offer an approximate description of the recoil- and Doppler-modified photoemission spectral lineshape as a practical tool in the analysis of HAXPES spectra of core-level photoemission. The approach is tested on the examples of carbon dioxide and pentane molecules. The C and O 1s photoelectron spectra of CO2 in gas phase were also measured at 2.3 and 7.0 keV photon energy at Synchrotron SOLEIL and the spectra were analyzed using the model description. The limitations and applicability of the approach to adsorbates, interfaces and solids is briefly discussed. [ABSTRACT FROM AUTHOR]

Using synchrotron radiation in the tender X-ray regime, a photoelectron spectrum showing the formation of single site double-core-hole pre-edge states, involving the K shell of the O atom in CO, has been recorded by means of high-resolution electron spectroscopy. The experimentally observed structures have been simulated, interpreted and assigned, employing state-of-the-art ab initio quantum chemical calculations, on the basis of a theoretical model, accounting for their so-called direct or conjugate character. Features appearing above the double ionization threshold have been reproduced by taking into account the strong mixing between multi-excited and continuum states. The shift of the σ* resonance below the double ionization threshold, in combination with the non-negligible contributions of multi-excited configurations in the final states reached, gives rise to a series of avoided crossings between the different potential energy curves. [ABSTRACT FROM AUTHOR]

We report unambiguous experimental and theoretical evidence of intramolecular photoelectron diffraction in the collective vibrational excitation that accompanies high-energy photoionization of gas-phase CF4, BF3, and CH4 from the 1s orbital of the central atom. We show that the ratios between vibrationally resolved photoionization cross sections (v-ratios) exhibit pronounced oscillations as a function of photon energy, which is the fingerprint of electron diffraction by the surrounding atomic centers. This interpretation is supported by the excellent agreement between first-principles static-exchange and time-dependent density functional theory calculations and high resolution measurements, as well as by qualitative agreement at high energies with a model in which atomic displacements are treated to first order of perturbation theory. The latter model allows us to rationalize the results for all the v-ratios in terms of a generalized v-ratio, which contains information on the structure of the above three molecules and the corresponding molecular cations. A fit of the measured v-ratios to a simple formula based on this model suggests that the method could be used to obtain structural information of both neutral and ionic molecular species. [ABSTRACT FROM AUTHOR]

A predictive understanding of soft x-ray near-edge absorption spectra of small molecules is an enduring theoretical challenge and of current interest for x-ray probes of molecular dynamics. We report the experimental absorption spectrum for the electron spectroscopy for chemical analysis (ESCA) molecule (ethyl trifluoroacetate) near the carbon 1s absorption edge between 285–300 eV. The ESCA molecule with four chemically distinct carbon sites has previously served as a theoretical benchmark for photoelectron spectra and now for photoabsorption spectra. We report a simple edge-specific approach for systematically expanding standard basis sets to properly describe diffuse Rydberg orbitals and the importance of triple excitations in equation-of-motion coupled-cluster calculations of the energy interval between valence and Rydberg excitations. [ABSTRACT FROM AUTHOR]

We present a combined experimental and theoretical study of the double-core-hole photoelectron spectrum obtained in isolated water molecules irradiated with hard x-rays above the oxygen K−2 threshold. States of the type O K−2V and multiply excited states are created by single-photon absorption and subsequent one-electron emission. A detailed analysis enabled by high experimental resolution reveals dissociative nuclear dynamics in the K−2V pre-edge states. At the binding energies above the K−2 double-ionization potential, a complex spectral pattern is observed and attributed to highly excited states involving multiple shake-up excitation processes with the aid of state-of-the-art theoretical calculations. A strong broadening due to the nuclear motion indicates a highly dissociative nature of these multiply excited states, in agreement with the theoretical analysis. [ABSTRACT FROM AUTHOR]

We have observed formation of Rydberg series superimposed on the Ar (L3M2,3M2,3) Auger electron spectral profile with photoexcitation just above the 2p−13/2 photoionization threshold. This is due to the recapture of photoelectrons induced by post-collision interaction between the Auger electron and photoelectron: Ar+ 2p−13/2 + e− → Ar+ 3p−2ml + e−. The intensity distribution of the angular momentum state resolved Rydberg peaks revealed prominent conjugate peaks due to angular momentum exchange between photoelectrons and Auger electrons in the process. In addition, we measured the 2p−13/2nl → 3p−2ml + e− resonant Auger spectra with high resolution below the 2p−13/2 threshold. Our results showed that conjugate shake-up/down 2p−13/2nd → 3p−2mp + e− processes are stronger than the direct 2p−13/2nd → 3p−2ms, (m−1)d + e− processes in the spectator Auger processes, implying a strong angular momentum exchange effect between photoelectron and Auger electron. [ABSTRACT FROM AUTHOR]

A photochemistry study on nitrous oxide making use of site-selective excitation of terminal nitrogen, central nitrogen, and oxygen 1s→3π excitations is presented. The resonant Auger decay which takes place following excitation can lead to dissociation of the N2O+ ion. To elucidate the nuclear dynamics, energy-resolved Auger electrons were detected in coincidence with the ionic dissociation products, and a strong dependence of the fragmentation pathways on the core-hole site was observed in the binding energy region of the first satellite states. A description based on the molecular orbitals as well as the correlation between the thermodynamical thresholds of ion formation and the first electronic states of N2O+ has been used to qualitatively explain the observed fragmentation patterns. [ABSTRACT FROM AUTHOR]

A new setup has been designed and built to study organometallic complexes in gas phase at the third-generation Synchrotron radiation sources. This setup consists of a new homemade computer-controlled gas cell that allows us to sublimate solid samples by accurately controlling the temperature. This cell has been developed to be a part of the high-resolution X-ray emission spectrometer permanently installed at the GALAXIES beamline of the French National Synchrotron Facility SOLEIL. To illustrate the capabilities of the setup, the cell has been successfully used to record high-resolution Kα emission spectra of gas-phase ferrocene F e ( C 5 H 5 ) 2 and to characterize their dependence with the excitation energy. This will allow to extend resonant X-ray emission to different organometallic molecules. [ABSTRACT FROM AUTHOR]

The formation of double core hole pre-edge states of the form 1s−12p−1(1,3P)σ*,nℓ for HCl, located on the binding energy scale as deep as 3 keV, has been investigated by means of a high resolution single channel electron spectroscopy technique recently developed for the hard X-ray region. A detailed spectroscopic assignment is performed based on ab initio quantum chemical calculations and by using a sophisticated fit model comprising regular Rydberg series. Quantum defects for the different Rydberg series are extracted and the energies for the associated double core hole ionization continua are extrapolated. Dynamical information such as the lifetime width of these double-core-hole pre-edge states and the slope of the related dissociative potential energy curves are also obtained. In addition, 1s−12p−1V−1nℓλn′ℓ′λ′ double shake-up transitions and double core hole states of the form 1s−12s−1(1,3S)σ*,4s are observed. [ABSTRACT FROM AUTHOR]

Auger decay spectra of CO subsequent to O 1s ionization with 549.85 eV photons, i.e. close to the top of the shape resonance, are presented. Their comparison with the normal Auger spectrum recorded at a photon energy well above the shape resonance reveals distinct features. In particular, in the energy region of the O 1s-1→b1Πand O 1s-1→a1Σ+ Auger transitions which are well known to consist of vibrational progressions, additional narrow lines are revealed by the spectra recorded at 549.85 eV. In a detailed fit analysis of these Auger spectra it was possible to show that the newly found lines do not exhibit the expected distortions caused by post-collision interaction. This observation identifies these lines as caused by a different mechanism, such as resonant Auger decay processes of doubly excited states. The transitions are assigned using energy and intensity arguments in combination with complementary angular distribution measurements for the Auger electrons. [ABSTRACT FROM AUTHOR]

This study focuses on the two C1s-to-LUMO (lowest unoccupied molecular orbital) excitations of the iso-dichloroethylene (H2C=CCl2) and the subsequent Auger decay. We investigate the effect of the two different carbon core excitations on the population of the cation produced after electronic relaxation. The resonant Auger spectra are interpreted by comparison to the valence shells photoionization spectrum and with the help of theoretical calculations. Several consequences of the core-hole localization on the electronic decay are observed. In particular, the resonant excitation of the C1s(CH2) to the LUMO leads to a large intensity increase in the region of the first satellite state, whereas no dramatic changes are observed for the C1s(CCl2) excitation. [ABSTRACT FROM AUTHOR]

Abstract: In this article, we present the X-ray absorption spectra of the three isomers of dichloroethylene C2H2Cl2 in the vicinity of the chlorine L 2 and L 3 edges. These isomers were excited along the first Cl2p to lowest unoccupied molecular orbital transition and an analysis of the corresponding resonant Auger spectra shows that the C–Cl bond can break before the electronic decay. An investigation of a possible Auger Doppler-like effect is also presented. [Copyright &y& Elsevier]

Abstract: In a detailed study of the vibrational distribution of the state reached after decay of core-to- excitation of N terminal, N central and O 1s core levels is reported. We observe a change in the relative intensity of bending versus stretching modes while scanning the photon energy across all three resonances. While this effect is known to be due to the Renner–Teller splitting in the core-excited states, we could derive that the antisymmetric stretching is excited mainly in the decay of the N terminal 1s-to- excitation. An explanation for such selectivity is provided in terms of interplay of vibrational structure on potential energy surfaces of different electronic states involved in the process. [ABSTRACT FROM AUTHOR]

Abstract: The present work aims at characterizing short-lived core-excited states of the OCS molecule based on the analysis of the vibrational fine structure and lineshape profiles of the high-resolution resonant Auger decay spectra recorded at the excitation energies along the resonance in the binding energy region 15–19eV. Very different behavior in terms of lineshape and resonant enhancement is observed for the , and final states. This is explained by (1) the variation in the C–O bond lengths for the states involved in the electronic relaxation and (2) different contributions in terms of Mulliken population to the molecular orbitals determining the electronic character of the corresponding states. Since the final-state geometries are known from a number of previous experiments and ab initio calculations, the geometry of the intermediate states can be predicted in analogy with e.g. the N2, CO2 and N2O molecules. [Copyright &y& Elsevier]

Tuning hard x-ray excitation energy along Cl 1s → σ∗ resonance in gaseous HCl allows manipulating molecular fragmentation in the course of the induced multistep ultrafast dissociation. The observations are supported by theoretical modeling, which shows a strong interplay between the topology of the potential energy curves, involved in the Auger cascades, and the so-called core-hole clock, which determines the time spent by the system in the very first step. The asymmetric profile of the fragmentation ratios reflects different dynamics of nuclear wave packets dependent on the photon energy. [ABSTRACT FROM AUTHOR]

The differential photoionization cross section ratio (ν = 1)/(ν = 0) for the symmetric stretching mode in the C 1s photoionization of CF4 was studied both theoretically and experimentally. We observed this ratio to differ from the Franck–Condon ratio and to be strongly dependent on the photon energy, even far from the photoionization threshold. The density-functional theory computations show that the ratio is significantly modulated by the diffraction of the photoelectrons by the neighbouring atoms at high photon energies. At lower energies, the interpretation of the first very strong maximum observed about 60 eV above the photoionization threshold required detailed calculations of the absolute partial cross sections, which revealed that the absolute cross section has two maxima at lower energies, which turn into one maximum in the cross section ratio because the maxima appear at slightly different energies in ν = 1 and ν = 0 cross sections. These two strong, low-energy continuum resonances originate from the trapping of the continuum wavefunction in the molecular potential of the surrounding fluorine atoms and from the outgoing electron scattering by them. [ABSTRACT FROM AUTHOR]

Born–Oppenheimer and Franck–Condon approximations are two major concepts in the interpretation of electronic excitations and modeling of spectroscopic data in the gas and condensed phases. We report large variations of the anisotropy parameter (β) for the fully resolved vibrational sub-states of the X2Πg electronic ground state of O+2 populated by participator resonant Auger decay following excitations of K-shell electrons into the σ☆ resonance by monochromatic x-rays. Decay spectra for light polarization directions parallel and perpendicular to the electron detection axis recorded at four different excitation energies in the vicinity of the O 1s → σ☆ transition are presented. Breakdown of the Born–Oppenheimer approximation is for the first time selectively observed for the lower vibrational sub-states, where two quantum paths—resonant and direct—leading to the same final cationic state exist. The higher vibrational sub-states can only be populated by resonant photoemission; hence no interference between these channels can occur. [ABSTRACT FROM AUTHOR]

X-ray photoemission spectroscopy is used in a great variety of research fields; one observable is the sample's stoichiometry. The stoichiometry can be deduced based on the expectation that the ionization cross sections for innershell Orbitals are independent of the molecular composition. Here we used chlorine-substituted ethanes in the gas phase to investigate the apparent carbon stoichiometry. We observe a nonstoichiometric ratio for a wide range of photon energies, the ratio exhibits x-ray-absorption fine structure spectroscopy (EXAFS)-like oscillations and hundreds of eV above the C\s ionization approaches a value far from 1. These effects can be accounted for by considering the scattering of the outgoing photoelectron, which we model by multiple-scattering EXAFS calculations, and by considering the effects of losses due to monopole shakeup and shakeoff and to intramolecular inelastic scattering processes. [ABSTRACT FROM AUTHOR]

Abstract: We report a detailed analysis of the electronic structure of methyl oxirane, including core-level photoelectron spectroscopy, X-ray absorption at both C and O K-shells, resonant Auger and normal Auger spectroscopy. The X-ray absorption spectra (XAS) around the C K-edge can be easily interpreted on the ground of the chemical shift between the carbon atoms with different chemical environments. The X-ray absorption data around the O K-edge are quite structureless, hinting for a likely fragmentation process (possibly implying a ring-opening reaction). In resonant Auger spectra obtained after excitation below both the C 1s and O 1s ionization thresholds we notice a predominance of spectator decay implying a strong mixing between empty molecular orbitals and Rydberg states. [Copyright &y& Elsevier]

A mixture of CF4 and CO gases is used to study photoelectron recoil effects extending into the tender x-ray region. In CF4, the vibrational envelope of the C 1s photoelectron spectrum becomes fully dominated by the recoil-induced excitations, revealing vibrational modes hidden from Franck-Condon excitations. In CO, using CF4 as an accurate energy calibrant, we determine the partitioning of the recoil-induced internal excitation energy between rotational and vibrational excitation. The observed rotational recoil energy is 2.88(28) times larger than the observed vibrational recoil energy, well in excess of the ratio of 2 predicted by the basic recoil model. The experiment is, however, in good agreement with the value of 2.68 if energy transfer via Coriolis coupling is included. [ABSTRACT FROM AUTHOR]

A combination of resonant inelastic x-ray scattering and resonant Auger spectroscopy provides complementary information on the dynamic response of resonantly excited molecules. This is exemplified for CH3I, for which we reconstruct the potential energy surface of the dissociative I 3d-2 double-core-hole state and determine its lifetime. The proposed method holds a strong potential for monitoring the hard x-ray induced electron and nuclear dynamic response of core-excited molecules containing heavy elements, where ab initio calculations of potential energy surfaces and lifetimes remain challenging. [ABSTRACT FROM AUTHOR]

Using synchrotron radiation and high-resolution electron spectroscopy, we have directly observed and identified specific photoelectrons from K−2V states in neon corresponding to simultaneous 1s ionization and 1s→valence excitation. The natural lifetime broadening of the K−2V states and the relative intensities of different types of shakeup channels have been determined experimentally and compared to ab initio calculations. Moreover, the high-energy Auger spectrum resulting from the decay of Ne2+K−2 and Ne+K−2V states as well as from participator Auger decay from Ne+K−1L−1V states, has been measured and assigned in detail utilizing the characteristic differences in lifetime broadenings of these core hole states. Furthermore, post collision interaction broadening of Auger peaks is clearly observed only in the hypersatellite spectrum from K−2 states, due to the energy sharing between the two 1s photoelectrons which favors the emission of one slow and one fast electron. [ABSTRACT FROM AUTHOR]