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Momenta of ions from diiodomethane molecules after multiple ionization by soft-X-ray free-electron-laser pulses are measured. Correlations between the ion momenta are extracted by covariance methods formulated for the use in multiparticle momentum-resolved ion time-of-flight spectroscopy. Femtosecond dynamics of the dissociating multiply charged diiodomethane cations is discussed and interpreted by using simulations based on a classical Coulomb explosion model including charge evolution.

The photoelectron circular dichroism (PECD) of the O 1s-photoelectrons of trifluoromethyloxirane(TFMOx) is studied experimentally and theoretically for different photoelectron kinetic energies. The experiments were performed employing circularly polarized synchrotron radiation and coincidentelectron and fragment ion detection using Cold Target Recoil Ion Momentum Spectroscopy. The corresponding calculations were performed by means of the Single Center method within the relaxed-core Hartree-Fock approximation. We concentrate on the energy dependence of the differential PECD of uniaxially oriented TFMOx molecules, which is accessible through the employed coincident detection. We also compare results for differential PECD of TFMOx to those obtained for the equivalent fragmentation channel and similar photoelectron kinetic energy of methyloxirane (MOx), studied in our previous work. Thereby, we investigate the influence of the substitution of the methyl-group by the trifluoromethyl-group at the chiral center on the molecular chiral response. Finally, the presently obtained angular distribution parameters are compared to those available in literature., 6 figs

We have used the FERMI free-electron laser to perform time-resolved photoelectron imaging experiments on a complex group of resonances near 15.38 eV in the absorption spectrum of molecular nitrogen, N2, under jet-cooled conditions. The new data complement and extend the earlier work of Fushitani et al. [Opt. Express 27, 19702–19711 (2019)], who recorded time-resolved photoelectron spectra for this same group of resonances. Time-dependent oscillations are observed in both the photoelectron yields and the photoelectron angular distributions, providing insight into the interactions among the resonant intermediate states. In addition, for most states, we observe an exponential decay of the photoelectron yield that depends on the ionic final state. This observation can be rationalized by the different lifetimes for the intermediate states contributing to a particular ionization channel. Although there are nine resonances within the group, we show that by detecting individual photoelectron final states and their angular dependence, we can identify and differentiate quantum pathways within this complex system.

Absorption of x-ray photons by atomic inner shells of light-element organics and biomolecules often leads to formation of dicationic electronic states and to molecular fragmentation. We investigated the x-ray-induced dissociation landscape of a representative medium-sized organic molecule, thiophene, by femtosecond x-ray pulses from the Super Photon Ring-8 GeV (SPring-8) Angstrom Compact Free-Electron Laser (SACLA). Holes, created in the sulfur 2p orbital by photoemission, were filled by the Auger process that created dicationic molecular states within a broad range of internal energies—a starting point particular to x-ray-induced dynamics. The evolution of the ionized molecules was monitored by a pump-probe experiment using a near-infrared (800 nm) laser pulse. Ion-ion coincidence and ion momentum analysis reveals enhanced yields of ionic fragments from multibody breakup of the ring, attributed to additional ionization of the highly excited fraction of the dicationic parent molecular states. The transient nature of the enhancement and its decay with about a 160-fs time constant indicate formation of an open-ring parent geometry and the statistical survival time of the parent species before the dissociation events. By probing specific Auger final states of transient, highly excited nature by near-infrared light, we demonstrate how pump-probe signatures can be related to the key features in dynamics during the early period of the x-ray-induced damage of organic molecules and biomolecules. (Less)

The photodissociation dynamics of strong-field ionized methyl iodide (\ce{CH3I}) were probed using intense extreme ultraviolet (XUV) radiation produced by the SPring-8 Angstrom Compact free electron LAser (SACLA). Strong-field ionization and subsequent fragmentation of CH3I was initiated by an intense femtosecond infrared (IR) pulse. The ensuing fragmentation and charge-transfer processes following multiple ionization by the XUV pulse at a range of pump-probe delays were followed in a multi-mass ion velocity-map imaging (VMI) experiment. Simultaneous imaging of a wide range of resultant ions allowed for additional insight into the complex dynamics by elucidating correlations between the momenta of different fragment ions using time-resolved recoil-frame covariance imaging analysis. The comprehensive picture of the photodynamics that can be extracted provides promising evidence that the techniques described here could be applied to study ultrafast photochemistry in a range of molecular systems at high count rates using state-of-the-art advanced light sources.

Journal of physics / B 54(4), 044001 (1-16) (2021). doi:10.1088/1361-6455/abd878, Using electron and ion spectroscopy, we studied the electron and nuclear dynamics in ~50 000-atom large krypton clusters, following excitation with an intense hard x-ray pulse. Beyond the single pulse experiment, we also present the results of a time-resolved, x-ray pump–near-infrared probe measurement that allows one to learn about the time evolution of the system. After core ionization of the atoms by x-ray photons, trapped Auger and secondary electrons form a nanoplasma in which the krypton ions are embedded, according to the already published scenario. While the ion data show expected features, the electron emission spectra miss the expected pump–probe delay-dependent enhancement except for a slight enhancement in the energy range below 2 eV. Theoretical simulations help to reveal that, due to the deep trapping potential of the ions during the long time expansion accompanied by electron–ion recombination, thermal emission from the transient nanoplasma becomes quenched., Published by IOP Publ., Bristol

The possibility of suddenly ionized molecules undergoing extremely fast electron hole (or hole) dynamics prior to significant structural change was first recognized more than 20 years ago and termed charge migration. The accurate probing of ultrafast electron hole dynamics requires measurements that have both sufficient temporal resolution and can detect the localization of a specific hole within the molecule. We report an investigation of the dynamics of inner valence hole states in isopropanol where we use an x-ray pump-x-ray probe experiment, with site and state-specific probing of a transient hole state localized near the oxygen atom in the molecule, together with an ab initio theoretical treatment. We record the signature of transient hole dynamics and make the first tentative observation of dynamics driven by frustrated Auger-Meitner transitions. We verify that the effective hole lifetime is consistent with our theoretical prediction. This state-specific measurement paves the way to widespread application for observations of transient hole dynamics localized in space and time in molecules and thus to charge transfer phenomena that are fundamental in chemical and material physics. (Less)

Physical review / A covering atomic, molecular, and optical physics and quantum information 101(2), 023412 (2020). doi:10.1103/PhysRevA.101.023412, We present a time-resolved study of disintegration within atomic clusters ionized by a hard-x-ray pulse of moderate fluence. It was performed with electron and ion spectroscopy, and complemented by theoretical simulations. The expanding clusters were probed with a near-infrared (NIR) laser pulse over a range of pump-probe delays from −4 to 10 ps. In addition to an increasing number of singly charged atomic ions, originating from the ionization of Rydberg atoms formed through electron-ion recombination, we observe a decrease of oligomer yields. The latter is due to the interaction of oligomers with the NIR probe pulse, leading to their dissociation. At time delays between −1 and 2 ps, efficient absorption of the NIR laser energy occurs, even though the NIR intensity is too low to trigger tuneling ionization of Ar atoms. Our observations are similar to earlier observations of the fragmentation behavior of clusters excited by soft-x-ray pulses. This indicates that the relaxation dynamics of x-ray-excited nano-objects are universal over a wide range of excitation photon energies., Published by Inst., Woodbury, NY

Bichromatic extreme-ultraviolet pulses from a seeded free-electron laser enable us to measure photoelectron angular distribution (PAD) as a function of the relative phase between the different wavelength components. The time-dependent multiconfiguration self-consistent-field (TD-MCSCF) methods are powerful multielectron computation methods to accurately simulate such photoionization dynamics from the first principles. Here we propose a method to evaluate the amplitude and phase of each ionization path, which completely determines the photoionization processes, using TD-MCSCF simulation results. The idea is to exploit the capability of TD-MCSCF to calculate the partial wave amplitudes specified by the azimuthal and magnetic angular momenta (l,m) and the m-resolved PAD. The phases of the ionization paths as well as the amplitudes of the paths resulting in the same (l,m) are obtained through global fitting of the expression of the asymmetry parameters to the calculated m-resolved PAD, which depends on the relative phase of the bichromatic field. We apply the present method to ionization of Ne by combined fundamental and second-harmonic XUV pulses, demonstrating that the extracted amplitudes and phases excellently reproduce the asymmetry parameters., Comment: 21 pages, 2 figures, 11 tables

Physical review / X Expanding access 10(2), 021052 (2020). doi:10.1103/PhysRevX.10.021052, A central motivation for the development of x-ray free-electron lasers has been the prospect of time-resolved single-molecule imaging with atomic resolution. Here, we show that x-ray photoelectron diffraction—where a photoelectron emitted after x-ray absorption illuminates the molecular structure from within—can be used to image the increase of the internuclear distance during the x-ray-induced fragmentation of an O$_2$ molecule. By measuring the molecular-frame photoelectron emission patterns for a two-photon sequential $K$-shell ionization in coincidence with the fragment ions, and by sorting the data as a function of the measured kinetic energy release, we can resolve the elongation of the molecular bond by approximately 1.2 a.u. within the duration of the x-ray pulse. The experiment paves the road toward time-resolved pump-probe photoelectron diffraction imaging at high-repetition-rate x-ray free-electron lasers., Published by APS, College Park, Md.

An accurate description of the interaction of intense hard X-ray pulses with heavy atoms, which is crucial for many applications of free-electron lasers, represents a hitherto unresolved challenge for theory because of the enormous number of electronic configurations and relativistic effects, which need to be taken into account. Here we report results on multiple ionization of xenon atoms by ultra-intense (about 1019 W/cm2) femtosecond X-ray pulses at photon energies from 5.5 to 8.3 keV and present a theoretical model capable of reproducing the experimental data in the entire energy range. Our analysis shows that the interplay of resonant and relativistic effects results in strongly structured charge state distributions, which reflect resonant positions of relativistically shifted electronic levels of highly charged ions created during the X-ray pulse. The theoretical approach described here provides a basis for accurate modeling of radiation damage in hard X-ray imaging experiments on targets with high-Z constituents., Availability of intense hard X-ray pulses allows exploration of multiple ionization effects in heavier elements. Here, the authors measure the complex charge state distributions of xenon and found a reasonable agreement by comparing with the model including the relativistic and resonance effects.

Author(s): Okunishi, M; Ito, Y; Sharma, V; Aktar, S; Ueda, K; Lucchese, RR; Dnestryan, AI; Tolstikhin, OI; Inoue, S; Matsui, H; Morishita, T | Abstract: Photoelectron momentum distributions (PEMDs) generated in strong-field ionization of randomly oriented CO2 molecules by intense infrared laser pulses at 1300-, 1450-, and 1650-nm wavelengths are measured experimentally and analyzed theoretically. The experimental PEMDs extracted along the outermost backward rescattering caustic are well reproduced by theoretical calculations based on the recently derived factorization formula with an analytical returning photoelectron wave packet (RWP). The sensitivity of the theoretical results to the target structure models used in the calculations is investigated. It is shown that RWPs obtained in the single-active-electron (SAE) approximation and by the Hartree-Fock method have only minor differences. On the other hand, differential cross sections (DCSs) for elastic scattering of a photoelectron on the parent molecular ion calculated by ab initio, SAE, and independent-atom model methods are considerably different. This difference almost disappears after averaging over molecular orientations, so the present experiment does not enable us to discriminate between the different target structure models. However, we show that such a discrimination should become possible by measuring PEMD with aligned molecules. This will provide an access to the rich target structure information contained in the DCS.

We have investigated the ionization and fragmentation of a metallo-endohedral fullerene, Sc3N@C80, using ultrashort (10 fs) x-ray pulses. Following selective ionization of a Sc (1s) electron (hν = 4.55 keV), an Auger cascade leads predominantly to either a vibrationally cold multiply charged parent molecule or multifragmentation of the carbon cage following a phase transition. In contrast to previous studies, no intermediate regime of C2 evaporation from the carbon cage is observed. A time-delayed, hard x-ray pulse (hν = 5.0 keV) was used to attempt to probe the electron transfer dynamics between the encapsulated Sc species and the carbon cage. A small but significant change in the intensity of Sc-containing fragment ions and coincidence counts for a delay of 100 fs compared to 0 fs, as well as an increase in the yield of small carbon fragment ions, may be indicative of incomplete charge transfer from the carbon cage on the sub-100 fs time scale.

X-ray free-electron lasers have, over the past decade, opened up the possibility of understanding the ultrafast response of matter to intense X-ray pulses. In earlier research on atoms and small molecules, new aspects of this response were uncovered, such as rapid sequences of inner-shell photoionization and Auger ionization. Here, we studied a larger molecule, buckminsterfullerene (C60), exposed to 640 eV X-rays, and examined the role of chemical effects, such as chemical bonds and charge transfer, on the fragmentation following multiple ionization of the molecule. To provide time resolution, we performed femtosecond-resolved X-ray pump/X-ray probe measurements, which were accompanied by advanced simulations. The simulations and experiment reveal that despite substantial ionization induced by the ultrashort (20 fs) X-ray pump pulse, the fragmentation of C60 is considerably delayed. This work uncovers the persistence of the molecular structure of C60, which hinders fragmentation over a timescale of hundreds of femtoseconds. Furthermore, we demonstrate that a substantial fraction of the ejected fragments are neutral carbon atoms. These findings provide insights into X-ray free-electron laser-induced radiation damage in large molecules, including biomolecules. X-ray pump–probe experiments reveal that the molecular structure of C60 molecules substantially delays their fragmentation following photoionization. This may help to understand X-ray laser-induced radiation damage on molecules.

International audience; Soft-x-ray free-electron-laser pulses were used to create highly charged molecular tetrabromothiophene species by sequential multiphoton ionization from bromine 3 dorbitals. The experiment was performed at the SACLA facility in Japan and the products of molecular dissociation were analyzed by means of multicoincidence momentum-resolved ion time-of-flight spectroscopy. Total charge states up to +13 atomic units were produced, creating a particular dissociation pattern for the carbon ions, a Coulomb implosion, due to the concerted forces by the surrounding heavy bromine ions. This behavior was explored both experimentally and by numerical molecular-dynamics simulations and the fingerprints of the Coulomb implosion were identified in both. In simulations, Coulomb implosion was predicted to be highly sensitive to the initial (thermal) motion of the atoms and, after including vibrational motion for several temperatures, good general agreement between the experiment and simulations was found. The agreement with the experiment was further improved by adding charge dynamics to the simulation, according to our point-charge dynamics model with empirical rate constants.

The recent availability of intense and ultrashort extreme ultraviolet sources opens the possibility to investigate ultrafast electronic relaxation processes in matter in an unprecedented regime. In this work we report on the observation of two-photon excitation of interatomic Coulombic decay (ICD) in neon dimers using the tunable intense pulses delivered by the free electron laser FERMI@Elettra. The unique characteristics of FERMI (narrow bandwidth, spectral stability, and tunability) allow one to resonantly excite specific ionization pathways and to observe a clear signature of the ICD mechanism in the ratio of the ion yield created by Coulomb explosion. The present experimental results are explained by \emph{ab initio} electronic structure and nuclear dynamics calculations.

We publish three Roadmaps on photonic, electronic and atomic collision physics in order to celebrate the 60th anniversary of the ICPEAC conference. Roadmap III focusses on heavy particles: with zero to relativistic speeds. Modern theoretical and experimental approaches provide detailed insight into the wide range of many-body interactions involving projectiles and targets of varying complexity ranging from simple atoms, through molecules and clusters, complex biomolecules and nanoparticles to surfaces and crystals. These developments have been driven by technological progress and future developments will expand the horizon of the systems that can be studied. This Roadmap aims at looking back along the road, explaining the evolution of the field, and looking forward, collecting nineteen contributions from leading scientists in the field., Journal of Physics B: Atomic, Molecular and Optical Physics, 52 (17), ISSN:1361-6455, ISSN:0368-3508, ISSN:0953-4075, ISSN:0022-3700

We have performed a full-dimensional theoretical study of vibrationally resolved photoelectron emission from the valence shell of the water molecule by using an extension of the static-exchange density functional theory that accounts for ionization as well as for vibrational motion in the symmetric stretching, antisymmetric stretching, and bending modes. At variance with previous studies performed in centrosymmetric molecules, where vibrationally resolved spectra are mostly dominated by the symmetric stretching mode, in the present case, all three modes contribute to the calculated spectra, including intermode couplings. We have found that diffraction of the ejected electron by the various atomic centers is barely visible in the ratios between vibrationally resolved photoelectron spectra corresponding to different vibrational states of the remaining H2O+ cation (the so-called v-ratios), in contrast to the prominent oscillations observed in K-shell ionization of centrosymmetric molecules, including those that only contain hydrogen atoms around the central atoms, e.g., CH4. To validate the conclusions of our work, we have carried out synchrotron radiation experiments at the SOLEIL synchrotron and determined photoelectron spectra and v-ratios for H2O in a wide range of photon energies, from threshold up to 150 eV. The agreement with the theoretical predictions is good.

We introduce and present a theory of interferometric measurement of a normal Auger decay lifetime in molecules. Molecular Auger interferometry is based on the coherent phase control of Auger dynamics in a two-color ($\ensuremath{\omega}/2\ensuremath{\omega}$) laser field. We show that, in contrast to atoms, in oriented molecules of certain point groups the relative $\ensuremath{\omega}/2\ensuremath{\omega}$ phase modulates the total ionization yield. A simple analytical formula is derived for the extraction of the lifetimes of Auger-active states from a molecular Auger interferogram, circumventing the need in either high-resolution or attosecond spectroscopy. We demonstrate the principle of the interferometric Auger lifetime measurement using inner-valence decay in ${\mathrm{CH}}_{3}\mathrm{F}$.

Journal of synchrotron radiation 26(4), 1017 - 1030 (2019). doi:10.1107/S1600577519003564, The xcalib toolkit has been developed to calibrate the beam profile of an X-ray free-electron laser (XFEL) at the focal spot based on the experimental charge state distributions (CSDs) of light atoms. Characterization of the fluence distribution at the focal spot is essential to perform the volume integrations of physical quantities for a quantitative comparison between theoretical and experimental results, especially for fluence-dependent quantities. The use of the CSDs of light atoms is advantageous because CSDs directly reflect experimental conditions at the focal spot, and the properties of light atoms have been well established in both theory and experiment. Theoretical CSDs are obtained using xatom, a toolkit to calculate atomic electronic structure and to simulate ionization dynamics of atoms exposed to intense XFEL pulses, which involves highly excited multiple core-hole states. Employing a simple function with a few parameters, the spatial profile of an XFEL beam is determined by minimizing the difference between theoretical and experimental results. The optimization procedure employing the reinforcement learning technique can automatize and organize calibration procedures which, before, had been performed manually. xcalib has high flexibility, simultaneously combining different optimization methods, sets of charge states, and a wide range of parameter space. Hence, in combination with xatom, xcalib serves as a comprehensive tool to calibrate the fluence profile of a tightly focused XFEL beam in the interaction region., Published by Wiley-Blackwell, [S.l.]

© 2018 IOP Publishing Ltd. The central (Nc) and terminal (Nt) nitrogen K-shell photoelectron spectra (PESs) of N2O molecules have been measured in the σ shape resonance energy region at temperatures of ∼300 and ∼630 K. Estimating vibrational populations based on the Boltzmann distribution at these temperatures, PESs of vibrationally ground and bending-excited levels in the initial electronic ground state were extracted. Vibrationally integrated partial cross sections and asymmetry parameters for ionization from vibrationally ground and bending-excited levels were obtained as a function of the incident photon energy by integrating PESs over the vibrational levels of the core-hole states. In Ncphotoionization, the shape resonance from the bending-excited level was found to be shifted to the lower photon energy side and to become narrower than that from the ground vibrational level. In Ntphotoionization from the bending-excited level, the downward shift of the resonance is more significant than that in Ncionization. These experimental findings are qualitatively consistent with theoretical predictions and suggest that the shape resonance associated with the Ntcore hole is more sensitive to the bending angle of the initial state than is the shape resonance associated with the Nccore hole. The asymmetry parameters for photoionization from the bending-excited level, however, showed almost the same behavior as those from the ground vibrational level for both K-shell photoionization channels and in the photon energy range studied here.

International audience; We show that electron and ion spectroscopy reveals the details of the oligomer formation in Ar clusters exposed to an x-ray free electron laser (XFEL) pulse, i.e., chemical dynamics triggered by x rays. With guidance from a dedicated molecular dynamics simulation tool, we find that van der Waals bonding, the oligomer formation mechanism, and charge transfer among the cluster constituents significantly affect ionization dynamics induced by an XFEL pulse of moderate fluence. Our results clearly demonstrate that XFEL pulses can be used not only to “damage and destroy” molecular assemblies but also to modify and transform their molecular structure. The accuracy of the predictions obtained makes it possible to apply the cluster spectroscopy, in connection with the respective simulations, for estimation of the XFEL pulse fluence in the fluence regime below single-atom multiple-photon absorption, which is hardly accessible with other diagnostic tools.

Interatomic Coulombic Decay (ICD) is a relaxation phenomenon, which takes place in weakly bound atomic and molecular systems, typically within a few to hundreds of femtoseconds depending on the system and the particular decay mechanism. The creation of ICD-active states requires the production of highly excited systems, usually populated by innershell ionization or excitation. To this end, XUV and X-ray radiation from synchrotrons was conventionally applied for the majority of experiments due to the desired state-selective ionization of certain sub-shells. The advent of Free-Electron Lasers (FELs) has enabled an entirely new class of experiments, which finally allow to trace ICD directly in the time domain due to the femtosecond pulse duration. Within this paper, the first time-resolved ICD measurement using an XUV-pump–XUV-probe scheme will be discussed in detail. The experiment was performed on neon dimers and ICD was triggered by removing a 2s electron from one of the neon atoms using a 58 eV pulse from the FEL in Hamburg (FLASH). The onset of ICD was probed with a delayed copy of the trigger pulse that further ionized one of the two Ne+ ions emerging after ICD. Thus, the delay-dependent yield of coincident Ne+ + Ne2+ ion pairs contains the lifetime of the 2s-innershell vacancy decaying via ICD. The result of 150 fs ± 50 fs is in good agreement with theory but only for those calculations that explicitly take nuclear motion into account.

The hitherto unexplored two-photon doubly excited states [Ne∗(2p-13s)]2 were experimentally identified using the seeded, fully coherent, intense extreme ultraviolet free-electron laser FERMI. These states undergo ultrafast interatomic Coulombic decay (ICD), which predominantly produces singly ionized dimers. In order to obtain the rate of ICD, the resulting yield of Ne2+ ions was recorded as a function of delay between the extreme ultraviolet pump and UV probe laser pulses. The extracted lifetimes of the long-lived doubly excited states, 390(-130/+450) fs, and of the short-lived ones, less than 150 fs, are in good agreement with ab initio quantum mechanical calculations.

Physical review letters 118(1), 013002 (2017). doi:10.1103/PhysRevLett.118.013002, Intense, circularly polarized extreme-ultraviolet and near-infrared (NIR) laser pulses are combined to double ionize atomic helium via the oriented intermediate He+(3p) resonance state. Applying angle-resolved electron spectroscopy, we find a large photon helicity dependence of the spectrum and the angular distribution of the electrons ejected from the resonance by NIR multiphoton absorption. The measured circular dichroism is unexpectedly found to vary strongly as a function of the NIR intensity. The experimental data are well described by theoretical modeling and possible mechanisms are discussed., Published by APS, College Park, Md.

International audience; Double-slit experiments illustrate proof for wave–particle complementarity. The essence of Einstein–Bohr's debate about wave–particle duality was whether the momentum transfer between a particle and a recoiling slit could mark the path, thus destroying the interference. We realized this recoiling double-slit gedanken experiment by resonant X-ray photoemission from molecular oxygen for geometries near equilibrium (coupled slits) and in a dissociative state far away from equilibrium (decoupled slits). Interference is observed in the former case, while the electron momentum transfer quenches the interference in the latter case.

The interplay between Franck–Condon and recoil-induced vibrational excitation in core-electron photoionization has been investigated using generalized Franck–Condon factors. Three models for the vibrational wave functions have been considered: the linear-coupling model, the harmonic oscillator, and the Morse oscillator. At every level it appears that the two processes can be treated as independent, and the total vibrational excitation energy is simply the sum of the excitation energies characteristic of the two processes. At the level of the linear coupling model, the vibrational excitation profile is exactly the convolution of the profiles for the two different processes; for the other levels of approximation the overall profile differs only slightly from the convolution. The results also show that the vibrational intensity ratio, R v = ( v = 1 ) / ( v = 0 ) , varies linearly with the vibrational excitation, but that the proportionality constant relating these two quantities is not ℏω2, as has been previously assumed, but ℏω1 (where ω1 and ω2 are the characteristic vibrational frequencies of the neutral and ionized molecules, respectively).

We have studied the dissociative ionization dynamics of formic acid molecules with intense femtosecond laser pulses centered at 800 nm, employing the ion–ion coincidence imaging technique. Fragmentation reactions originating from both singly and doubly charged parent formic acid ions are observed. In this paper the kinetic energy distributions of several different ionic fragments will be presented. A clear difference in the kinetic energy distributions is observed between ionic fragments originating from the dissociation of the singly charged parent ion and those from the Coulomb explosion of the doubly charged parent ion. Channels exhibiting the emission of neutral hydrogen and channels exhibiting intra molecular hydrogen migration will also be discussed. We present a combined theoretical and experimental study to get to an understanding of the hydrogen migration mechanism at the molecular level.

Using electron spectroscopy, we investigated the nanoplasma formation process generated in xenon clusters by intense soft x-ray free electron laser (FEL) pulses. We found clear FEL intensity dependence of electron spectra. Multistep ionization and subsequent ionization frustration features are evident for the low FEL-intensity region, and the thermal electron emission emerges at the high FEL intensity. The present FEL intensity dependence of the electron spectra is well addressed by the frustration parameter introduced by Arbeiter and Fennel [New J. Phys. 13, 053022 (2011)].

Upon exposure to ultra-intense, hard X-ray pulses, polyatomic molecules containing one heavy atom reach a much higher degree of ionization than do individual heavy atoms, contrary to previous assumptions. X-ray free-electron lasers offer many new applications such as the ability to structurally probe fast biological processes. This requires the use of hard and intense X-ray pulses, but the behaviour of matter under such conditions has not been fully explored. Artem Rudenko et al. show that when exposing small polyatomic molecules that contain one heavy atom to hard X-ray pulses with ultra-high intensities, the response is qualitatively different from what is seen in experiments carried out under less extreme conditions. The observed ionization of the molecule is considerably enhanced compared to that of an individual heavy atom under the same conditions, owing to ultrafast charge transfer within the molecule that replenishes the electrons removed from the heavy atom, enabling further ionization. Being able to account for this effect will aid further use of X-ray free-electron lasers for studying biological systems. X-ray free-electron lasers enable the investigation of the structure and dynamics of diverse systems, including atoms, molecules, nanocrystals and single bioparticles, under extreme conditions1,2,3,4,5,6,7. Many imaging applications that target biological systems and complex materials use hard X-ray pulses with extremely high peak intensities (exceeding 1020 watts per square centimetre)3,5. However, fundamental investigations have focused mainly on the individual response of atoms and small molecules using soft X-rays with much lower intensities8,9,10,11,12,13,14,15,16,17. Studies with intense X-ray pulses have shown that irradiated atoms reach a very high degree of ionization, owing to multiphoton absorption8,12,13,18, which in a heteronuclear molecular system occurs predominantly locally on a heavy atom (provided that the absorption cross-section of the heavy atom is considerably larger than those of its neighbours) and is followed by efficient redistribution of the induced charge14,15,16,17,19,20. In serial femtosecond crystallography of biological objects—an application of X-ray free-electron lasers that greatly enhances our ability to determine protein structure2,3—the ionization of heavy atoms increases the local radiation damage that is seen in the diffraction patterns of these objects21,22 and has been suggested as a way of phasing the diffraction data23,24. On the basis of experiments using either soft or less-intense hard X-rays14,15,16,17,18,19,25, it is thought that the induced charge and associated radiation damage of atoms in polyatomic molecules can be inferred from the charge that is induced in an isolated atom under otherwise comparable irradiation conditions. Here we show that the femtosecond response of small polyatomic molecules that contain one heavy atom to ultra-intense (with intensities approaching 1020 watts per square centimetre), hard (with photon energies of 8.3 kiloelectronvolts) X-ray pulses is qualitatively different: our experimental and modelling results establish that, under these conditions, the ionization of a molecule is considerably enhanced compared to that of an individual heavy atom with the same absorption cross-section. This enhancement is driven by ultrafast charge transfer within the molecule, which refills the core holes that are created in the heavy atom, providing further targets for inner-shell ionization and resulting in the emission of more than 50 electrons during the X-ray pulse. Our results demonstrate that efficient modelling of X-ray-driven processes in complex systems at ultrahigh intensities is feasible.

We investigate the resonance-like enhancement (RLE) in high-order above-threshold ionization (ATI) spectra of the polyatomic molecules ${\mathrm{C}}_{2}{\mathrm{H}}_{4}$ and ${\mathrm{C}}_{2}{\mathrm{H}}_{6}$. In the spectrum-intensity maps, strong and weak RLE areas emerge alternatively for both ${\mathrm{C}}_{2}{\mathrm{H}}_{4}$ and ${\mathrm{C}}_{2}{\mathrm{H}}_{6}$ but in different sequences. Theoretical calculations using the strong-field approximation reproduce the experimental observation and analysis shows that the different characteristics of the two molecules can be attributed to interference effects of molecular orbitals with different symmetries. For ${\mathrm{C}}_{2}{\mathrm{H}}_{4}$, the RLE structures are attributed to C--C centers of the highest occupied molecular orbital (HOMO) orbital. For ${\mathrm{C}}_{2}{\mathrm{H}}_{6}$, in contrast, the C--C centers of the HOMO and HOMO-1 orbitals do not contribute to the RLE due to destructive interference but the hydrogen centers of the bonding HOMO-1 orbital give rise to the multiple RLE regions. In addition, clear experimental evidence of the existence of two types of the RLE and their dependence on the parity of ground state is shown. Our result, which strongly supports the channel-closing mechanism of the RLE, for the first time reveals the important role of low-lying orbitals and the differing roles of different atomic centers in the high-order ATI spectrum of molecules.

International audience; Ultrafast electron transfer in dissociating iodomethane and fluoromethane molecules was studied at the Linac Coherent Light Source free-electron laser using an ultraviolet-pump, X-ray-probe scheme. The results for both molecules are discussed with respect to the nature of their UV excitation and different chemical properties. Signatures of long-distance intramolecular charge transfer are observed for both species, and a quantitative analysis of its distance dependence in iodomethane is carried out for charge states up to I21+. The reconstructed critical distances for electron transfer are in good agreement with a classical over-the-barrier model and with an earlier experiment employing a near-infrared pump pulse.

In high-intensity laser light, matter can be ionized by direct multiphoton absorption even at photon energies below the ionization threshold. However on tuning the laser to the lowest resonant transition, the system becomes multiply excited, and more efficient, indirect ionization pathways become operative. These mechanisms are known as interatomic Coulombic decay (ICD), where one of the species de-excites to its ground state, transferring its energy to ionize another excited species. Here we show that on tuning to a higher resonant transition, a previously unknown type of interatomic Coulombic decay, intra-Rydberg ICD occurs. In it, de-excitation of an atom to a close-lying Rydberg state leads to electron emission from another neighbouring Rydberg atom. Moreover, systems multiply excited to higher Rydberg states will decay by a cascade of such processes, producing even more ions. The intra-Rydberg ICD and cascades are expected to be ubiquitous in weakly-bound systems exposed to high-intensity resonant radiation., 原子の集団が数珠つなぎに電子を放出する! : 極紫外自由電子レーザーで誘起される新現象解明. 京都大学プレスリリース. 2016-12-12.

Most large molecules are chiral in their structure: they exist as two enantiomers, which are mirror images of each other. Whereas the rovibronic sublevels of two enantiomers are almost identical (neglecting a minuscular effect of the weak interaction), it turns out that the photoelectric effect is sensitive to the absolute configuration of the ionized enantiomer. Indeed, photoionization of randomly oriented enantiomers by left or right circularly polarized light results in a slightly different electron flux parallel or antiparallel with respect to the photon propagation direction—an effect termed photoelectron circular dichroism (PECD). Our comprehensive study demonstrates that the origin of PECD can be found in the molecular frame electron emission pattern connecting PECD to other fundamental photophysical effects such as the circular dichroism in angular distributions (CDAD). Accordingly, distinct spatial orientations of a chiral molecule enhance the PECD by a factor of about 10.

X-ray free-electron lasers provide unique opportunities for exploring ultrafast dynamics and for imaging the structures of complex systems. Understanding the response of individual atoms to intense X-rays is essential for most free-electron laser applications. First experiments have shown that, for light atoms, the dominant interaction mechanism is ionization by sequential electron ejection, where the highest charge state produced is defined by the last ionic state that can be ionized with one photon. Here, we report an unprecedentedly high degree of ionization of xenon atoms by 1.5 keV free-electron laser pulses to charge states with ionization energies far exceeding the photon energy. Comparing ion charge-state distributions and fluorescence spectra with state-of-the-art calculations, we find that these surprisingly high charge states are created via excitation of transient resonances in highly charged ions, and predict resonance enhanced absorption to be a general phenomenon in the interaction of intense X-rays with systems containing high-Z constituents. Researchers create high ionization states, up to Xe36+, using 1.5 keV free-electron laser pulses. The higher than expected ionization may be due to transient resonance-enhanced absorption and the effect may play an important role in interactions of intense X-rays with high-Z elements and radiation damage.

Photoemission from free molecules in the gas phase results in a complex spectral structure of electronic, vibrational and rotational transitions. In this review, the effects that can alter this structure and particularly the branching ratios in photoelectron spectra at the kinetic energies well above the ionization thresholds are considered. Simplified models that have nevertheless been found to describe the observations well are presented for photoelectron vibrational and rotational recoil, rotational Doppler broadening, photoelectron scattering and Cohen–Fano type interference phenomena. Experimental examples are shown together with the models. Some future developments and applications of the recoil-related phenomena are briefly considered.

We calculated ionization potentials (IPs) to create single core–hole states and double ionization potentials (DIPs) to create double core–hole (DCH) states for a series of trihalosilyl–trimethylsilyl molecules bridged with hydrocarbons. From the calculated DIPs, IPs, and the hole–hole repulsion energies, we extracted the excess relaxation energies for the creation of DCHs at a single atomic site and interatomic relaxation energies for the creation of DCHs at two different sites. These excess and interatomic relaxation energies depend solely on the chemical environment around the atom(s) with core hole(s). We found that the interatomic relaxation is almost blocked by a dimethylene group (–CH 2 CH 2 –).

In an aim to create a "sharp" molecular knife, we have studied site-specific fragmentation caused by Si:2p core photoionization of bridged trihalosilyltrimethylsilyl molecules in the vapor phase. Highly site-specific bond dissociation has been found to occur around the core-ionized Si site in some of the molecules studied. The site specificity in fragmentation and the 2p binding energy difference between the two Si sites depend in similar ways on the intersite bridge and the electronegativities of the included halogen atoms. The present experimental and computational results show that for efficient "cutting" the following conditions for the two atomic sites to be separated by the knife should be satisfied. First, the sites should be located far from each other and connected by a chain of saturated bonds so that intersite electron migration can be reduced. Second, the chemical environments of the atomic sites should be as different as possible.

Unlike metallic elements, rare-gas atoms remain non-metallic even if they are condensed. However, once rare-gas clusters are irradiated by extreme ultraviolet free electron laser (EUV-FEL) pulses with slightly higher energy than their ionization potential, they exhibit metallic-like behaviors because the ionization takes place sequentially within the clusters owing to the huge valence electron ionization cross section in the EUV regime. In this work Ar and Xe clusters were produced by pulsed supersonic jets, and the cluster beams were crossed synchronously with focused EUV-FEL beams ejected from the SCSS test accelerator in Japan. We measured time-of-flight (TOF) mass spectra and kinetic energy distribution (KED) of daughter ions produced via Coulomb explosion by using three dimensional (3D) momentum imaging spectrometer. The metallic-like nature is evidenced not only by widely spread charge distributions within the cluster but also by enhanced positive surface charges surrounded by quasi-free electron clouds.

We have investigated dissociative double ionization of formic acid by intense 100 fs laser pulses at 800 nm, using ion–ion coincidence momentum spectroscopy. Neither changing the laser power nor switching the laser polarization from linear to circular affected energy distributions of the ion pair. This observation is interpreted as implying the occurrence of sequential enhanced ionization.

We have theoretically investigated the double core-hole (DCH) states of the open-shell molecules and examined the possibility of DCH spectroscopy by means of X-ray two-photon photoelectron spectroscopy (XTPPS). Energies of many DCH states were obtained by the CASSCF calculations and the generalized intra- and interatomic relaxation energies were evaluated. We show that XTPPS can extract these quantities by the measurement of single and double core-hole ionization potentials. We discuss the influence of chemical environment on the DCH states with two holes at the same atomic site and at two different atomic sites., 17 pages. To appear in Chem.Phys.Lett

Molecular-frame photoelectron angular distributions (MFPADs) for CF4 in the fluorine K-shell ionization region have been measured at three photon energies 705, 725 and 775 eV. The molecular axis was defined by the momenta of the F + – CF 3 + ions detected in coincidence. The MFPADs were compared with ab initio calculations using the time dependent density functional theory. The results of a calculation assuming a localized F 1s core-hole agree better with the observed MFPADs than the results of a calculation using a delocalized core-hole, especially for 775 eV.

Methane and deuteromethane molecules were core ionized using synchrotron radiation, and the ionic fragments from the molecular dissociation were detected in coincidence with the Auger electrons. The electron–ion coincidence spectra are analysed in terms of partial ion yields and ion kinetic energy distributions, both as functions of electron kinetic energy. The dependence of the fragmentation patterns on the electronic character of the Auger final states as well as on the excess energy available for dissociating the molecule is studied. The analysis reveals marked differences in the dissociation of the 2a−21 and 2a−111t−12 states, interpreted as an 'excess-energy-dependent' concerted dissociation process for the 2a−21 state and an 'electronic-state-dependent' sequential process for the 2a−111t−12 state.

Core-level photoemission from N2 can be considered an analogue of Young’s double-slit experiment (YDSE) in which the double-slit is replaced by a pair of N 1s orbitals. The measured ratio between the 1 σ g and 1 σ u photoionization cross-sections oscillates as a function of photoelectron momentum, due to two-center YDSE interference, exhibiting a remarkable dependence on the vibrational sub-levels of the core ionized state. We theoretically demonstrate that the recoil of the photoelectron given to the ionized N atom strongly influences this interference pattern. The reason for this is that the momentum transfer affects the phases of the photoionization amplitudes.

Electron spectroscopy has been employed to probe the transition between the multiphoton ionization and tunneling ionization regimes upon irradiation of linear alcohol molecules, methanol, ethanol and 1-propanol, by 150 fs long pulses of linearly polarized 800 nm laser light at peak intensities up to 150 TW cm −2 . Somewhat unexpectedly, electron energy distributions reveal that the ionization dynamics proceed in atom-like manner and are adequately described by the conventional Keldysh–Faisal–Reiss model of atomic ionization.

Vibrationally resolved Nc and Nt K-shell photoelectron spectra of the dinitrogen oxide have been studied experimentally and theoretically. Vibrational frequencies for the Nc and Nt 1s ionized state ...

A projection method is developed for extracting the nondipole contribution from the molecular frame photoelectron angular distributions of linear molecules. A corresponding convenient parametric form for the angular distributions is derived. The analysis was performed for the N 1s photoionization of the NO molecule a few eV above the ionization threshold. No detectable nondipole contribution was found for the photon energy of 412 eV.

The analysis of the molecular-frame photoelectron angular distributions (MFPADs) is discussed within the dipole approximation. The general expressions are reviewed and strategies for extracting the maximum amount of information from different types of experimental measurements are considered. The analysis of the N 1s photoionization of NO is given to illustrate the method.

Dissociative ionization of methanol induced by ultrashort laser pulses has been studied at wavelengths of 400 nm and 800 nm with moderate intensity (1012−13 W/cm2). The laser power dependence of ionic species shows that multi photon ionization causes an excitation with a total energy from 11 to 15 eV. Comparing the current results with those of conventional VUV photodissociation experiments, we conclude that the molecules are excited to the X, A, B and C states of the ion, resulting in the CH4O+, CH3O+, CH 3 + and CHO+ ions, respectively.