Photo- and auger-electron recoil induced dynamics of interatomic Coulombic decay.

At photon energies near the Ne K edge it is shown that for 1s ionization the Auger electron, and for 2s ionization the fast photoelectron, launch vibrational wave packets in a Ne dimer. These wave packets then decay by emission of a slow electron via interatomic Coulombic decay (ICD). The measured and computed ICD electron spectra are shown to be significantly modified by the recoil induced nuclear motion.

Two-source double-slit interference in angle-resolved high-energy above-threshold ionization spectra of diatoms.

When an electron from a diatomic molecule undergoes tunneling-rescattering ionization, a novel form of destructive interference can be realized that involves all four geometric orbits that are available to the electron when it is freed, because both ionization and rescattering may take place at the same or at different centers. We find experimentally and confirm theoretically that in orientation-averaged angle-resolved high-order above-threshold ionization spectra the corresponding destructive interference is visible for O_{2} but not for N_{2}. This effect is different from the suppression of ionization that is well known to occur for O_{2}.

Cold-target recoil-ion momentum spectroscopy for diagnostics of high harmonics of the extreme-ultraviolet free-electron laser light source at SPring-8.

We have developed a cold-target recoil-ion momentum spectroscopy apparatus dedicated to the experiments using the extreme-ultraviolet light pulses at the free-electron laser facility, SPring-8 Compact SASE Source test accelerator, in Japan and used it to measure spatial distributions of fundamental, second, and third harmonics at the end station.

Is CO carbon KVV Auger electron emission affected by the photoelectron?

Angular distributions (ADs) of O+ fragments from C 1s photoexcited CO detected in coincidence with carbon KVV Auger electrons emitted in the horizontal direction were measured at photon energies of 298, 305, 320, and 450 eV. At 450 eV, the ADs are polarization-independent and coincide with the molecular-frame Auger electron angular distribution. All measured ADs can be rationalized as a product of the same molecular-frame Auger electron angular distribution and the axial selectivity in the photoionization process. Thus the interaction between the photoelectron and the Auger electron for the normal Auger decay of CO can be neglected, and the two-step model is a good approximation.

Experimental retrieval of target structure information from laser-induced rescattered photoelectron momentum distributions.

We have measured two-dimensional photoelectron momentum spectra of Ne, Ar, and Xe generated by 800-nm, 100-fs laser pulses and succeeded in identifying the spectral ridge region (back-rescattered ridges) which marks the location of the returning electrons that have been backscattered at their maximum kinetic energies. We demonstrate that the structural information, in particular the differential elastic scattering cross sections of the target ion by free electrons, can be accurately extracted from the intensity distributions of photoelectrons on the ridges, thus effecting a first step toward laser-induced self-imaging of the target, with unprecedented spatial and temporal resolutions.

Molecular-frame angular distributions of resonant CO:C(1s) Auger electrons.

The molecular-frame angular distributions of resonantly excited CO:C(1s) --> pi* Auger electrons were determined using angle-resolved electron-ion coincidence spectroscopy in combination with a novel transformation procedure. Our new methodology yields full three-dimensional electron angular distributions with high energy resolution from the measurement of electrons at only two angles. The experimentally determined distributions are well reproduced by calculations performed in a simple one-center approximation, allowing an unambiguous identification of several overlapping Auger lines.

Combining high mass resolution and velocity imaging in a time-of-flight ion spectrometer using pulsed fields and an electrostatic lens.

We describe a momentum resolving time-of-flight ion mass spectrometer that combines a high mass resolution, a velocity focusing condition for improved momentum resolution, and field-free conditions in the source region for high resolution electron detection. It is used in electron-ion coincidence experiments to record multiple ionic fragments produced in breakup reactions of small to medium sized molecules, such as F(3)SiCH(2)CH(2)Si(CH(3))(3). These breakup reactions are caused by soft x rays or intense laser fields. The ion spectrometer uses pulsed extraction fields, an electrostatic lens, and a delay line detector to resolve the position. Additionally, we describe a simple analytical method for calculating the momentum from the measured hit position and the time of flight of the ions.

Ionization of linear alcohols by strong optical fields.

We have experimentally probed the strong-field ionization dynamics of gas-phase linear alcohols, methanol, ethanol, and 1-propanol, by irradiating them with intense, femtosecond-duration laser pulses of 800 and 400 nm wavelength. Specifically, we make high resolution measurements of the energies of electrons that are ionized by the action of the optical field. Our electron spectroscopy measurements enable us to bifurcate the dynamics into multiphoton ionization and tunneling ionization regimes. In the case of 800 nm irradiation, such bifurcation into different ionization regimes is reasonably rationalized within the framework of the adiabaticity parameter based on the original Keldysh-Faisal-Reiss model of atomic ionization, without recourse to any structure-dependent modifications to the theory. In that sense, our 800 nm spectroscopy indicates that the linear alcohols exhibit atom-like properties as far as strong field ionization dynamics in the multiphoton ionization and tunneling regimes are concerned. We also explore the limitations of this atom-like picture by making measurements with 400 nm photons wherein the ponderomotive potential experienced by the ionized electrons is much less than the photon energy; effects that are purely molecular then appear to influence the strong field dynamics.

Probing molecular symmetry effects in the ionization of N2 and O2 by intense laser fields.

High-resolution electron spectroscopy is used to explore the role played by molecular symmetry in determining the morphology of the energy spectra of electrons ejected when N2 and O2 are irradiated by intense laser fields. In O2, the low-energy part of the electron spectrum is curtailed due to the destructive interference brought about by the antibonding nature of the O2 valence orbital. The high-energy tail of the spectrum is also suppressed by virtue of electron rescattering being of little consequence in O2. In contrast, in N2, which has a bonding valence orbital, the electron dynamics follow the pattern that has been established for atomic ionization in strong optical fields.

Probing the valence character of O 1s-->Rydberg excited O2 by participator Auger decay measurements and partial ion yield spectroscopy following x-ray absorption.

The valence character of O 1s-->Rydberg excited O2 is investigated by means of participator Auger decay spectroscopy, performed at selected photon energies across the K-shell resonance region, and by means of partial ion yield x-ray absorption spectroscopy. For several of the excitation energies studied, the authors find substantial sigma*(4Sigmau-, 2Sigmau-) valence character being mixed with nssigma and npsigma (4Sigmau-, 2Sigmau-) Rydberg states. An experimental indication of a coupling between the channels associated with quartet and doublet ion cores is considered and discussed. New spectroscopic constants are derived for the singly ionized X 2Pig state of O2 based on the observation of at least 20 vibrational sublevels.

Experimental evidence of interatomic coulombic decay from the auger final states in argon dimers.

Interatomic Coulombic decay (ICD) from an Auger-final dicationic state is observed in the Ar dimer. A 2p inner-shell vacancy created by photoionization is replaced with 3s and 3p vacancies via intra-atomic Auger decay. The Auger-final dicationic state is subject to ICD in which one of the 3p electrons in the same Ar atom fills the 3s vacancy while one of the 3p electrons from the neighboring Ar atom is emitted as an ICD electron. This ICD process is unambiguously identified by electron-ion-ion coincidence spectroscopy in which the kinetic energy of the ICD electron and the kinetic energy release between Ar+ and Ar2+ are measured in coincidence.

Symmetry-dependent vibrational excitation in N 1s photoionization of N2: experiment and theory.

We have measured the vibrational structures of the N 1s photoelectron mainline and satellites of the gaseous N2 molecule with the resolution better than 75 meV. The gerade and ungerade symmetries of the core-ionized (mainline) states are resolved energetically, and symmetry-dependent angular distributions for the satellite emission allow us to resolve the Sigma and Pi symmetries of the shake-up (satellite) states. Symmetry-adapted cluster-expansion configuration-interaction calculations of the potential energy curves for the mainline and satellite states along with a Franck-Condon analysis well reproduce the observed vibrational excitation of the bands, illustrating that the theoretical calculations well predict the symmetry-dependent geometry relaxation effects. The energies of both mainline states and satellite states, as well as the splitting between the mainline gerade and ungerade states, are also well reproduced by the calculation: the splitting between the satellite gerade and ungerade states is calculated to be smaller than the experimental detection limit.

Symmetry-resolved absorption spectra of vibrationally excited CO2 molecules.

Symmetry-resolved x-ray absorption spectroscopy has been first carried out on high-temperature molecules. From the angle-resolved ion yield spectra of CO2 both at room temperature and at 430 degrees C, symmetry-resolved absorption profiles of the C 1s(-1) 2pi(u) and O 1s(-1) 2pi(u) resonances have been extracted for the vibrational ground state molecules and bending-vibration excited ones. The profiles change dramatically between them, and the Renner-Teller effect becomes more evident for the vibrationally excited molecules. The effects of the multimode vibronic coupling are suggested for the O 1s(-1) 2pi(u) and O 1s(-1) 3s sigma(g) resonances.

Violation of the Franck-Condon principle due to recoil effects in high energy molecular core-level photoionization.

Carbon 1s photoelectron spectra of methane are measured over a photon energy range between 480 eV and 1200 eV. Additional components appear between the individual symmetric stretching vibrational components and are attributed to the excitations of asymmetric stretching and bending vibrations due to recoil of the high-energy photoelectron emission. This recoil effect is the evidence for the violation of the Franck-Condon principle which states that neither the positions nor the momenta of the nuclei change during the ionization event.

Intramolecular electron scattering and electron transfer following autoionization in dissociating molecules.

Resonant Auger decay of core-excited molecules during ultrafast dissociation leads to a Doppler shift of the emitted electrons depending on the direction of the electron emission relative to the dissociation axis. We have investigated this process by angle-resolved electron-fragment ion coincidence spectroscopy. Electron energy spectra for selected emission angles for the electron relative to the molecular axis reveal the occurrence of intermolecular electron scattering and electron transfer following the primary emission. These processes amount to approximately 25% of the resonant atomic Auger intensity emitted in the studied transition.

Sudden interchannel interaction in the Tl 6p ionization above the 5d threshold

The linear magnetic dichroism in the angular distribution of Tl 5d and 6p photoelectrons and their dynamical spin polarization have been measured between hnu = 30 and 50 eV. In contrast to the Xe 5p photoionization at the 4d threshold, our results show that above the Tl 5d threshold strong interchannel coupling effects induce a sudden increase in the asymptotic phase difference of the s and d waves for the Tl 6p ionization. This shows that the valence excitation is different for resonant (Xe 4d) and nonresonant (Tl 5d) excitation from subvalence shells.