James Harries

Compact XFEL and AMO sciences: SACLA and SCSS

The concept, design and performance of Japans compact free-electron laser (FEL) facilities, the SPring-8 Compact SASE Source test accelerator (SCSS) and SPring-8 Angstrom Compact free electron LAser (SACLA), and their applications in mainly atomic, molecular and optical science are reviewed. At SCSS, intense, ultrafast FEL pulses at extreme ultraviolet (EUV) wavelengths have been utilized for investigating various multi-photon processes in atoms, molecules and clusters by means of ion and electron spectroscopy. The quantum optical effect superfluorescence has been observed with EUV excitation. A pump?probe technique combining FEL pulses with near infrared laser pulses has been realized to study the ultrafast dynamics of atoms, molecules and clusters in the sub-picosecond regime. At SACLA, deep inner-shell multi-photon ionization by intense x-ray FEL pulses has been investigated. The development of seeded FEL sources for producing transversely and temporally coherent light, as well as the expected impact on advanced science are discussed.

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.

Recoil excitation of vibrational structure in the carbon 1s photoelectron spectrum of CF4

The carbon 1s photoelectron spectrum of CF4 measured at photon energies from 330 to 1500 eV shows significant contributions from nonsymmetric vibrational modes. These increase linearly as the photon energy increases. The excitation of these modes, which is not predicted in the usual Franck-Condon point of view, arises from the recoil momentum imparted to the carbon atom in the ionization process. A theory is presented for quantitative prediction of the recoil effect; the predictions of this theory are in agreement to the measurements. The experiments also yield the vibrational frequencies of the symmetric and asymmetric stretching modes in core-ionized CF4, the change in CF bond length upon ionization, -0.61 pm, and the Lorentzian linewidth of the carbon 1s hole, 67 meV.

Evidence of interatomic Coulombic decay in ArKr after Ar 2p Auger decay

We have identified interatomic Coulombic decay (ICD) processes in the ArKr dimer following Ar 2p Auger decay, using momentum-resolved electron–ion–ion coincidence spectroscopy and simultaneously determining the kinetic energy of the ICD electron and the KER between Ar 2+ and Kr + . We find that the spin-conserved ICD processes in which Ar 2+ (3p −3 3d) 1 Pa nd 3 P decay to Ar 2+ (3p −2 ) 1 Da nd 3 P, respectively, ionizing the Kr atom, are significantly stronger than the spin-flip ICD processes in which Ar 2+ (3p −3 3d) 1 Pa nd 3 P decay to Ar 2+ (3p −2 ) 3 Pa nd 1 D, respectively. (Some figures in this article are in colour only in the electronic version)

Inner-shell excitation spectroscopy and fragmentation of small hydrogen-bonded clusters of formic acid after core excitations at the oxygen K edge

Inner-shell excitation spectra and fragmentation of small clusters of formic acid have been studied in the oxygen K-edge region by time-of-flight fragment mass spectroscopy. In addition to several fragment cations smaller than the parent molecule, we have identified the production of HCOOH.H+ and H3O+ cations characteristic of proton transfer reactions within the clusters. Cluster-specific excitation spectra have been generated by monitoring the partial ion yields of the product cations. Resonance transitions of O1s(C[double bond]O/OH) electrons into pi(CO)* orbital in the preedge region were found to shift in energy upon clusterization. A blueshift of the O1s(C[double bond]O)-->pi(CO)* transition by approximately 0.2 eV and a redshift of the O1s(OH)-->pi(CO)* by approximately 0.6 eV were observed, indicative of strong hydrogen-bond formation within the clusters. The results have been compared with a recent theoretical calculation, which supports the conclusion that the formic-acid clusters consist of the most stable cyclic dimer andor trimer units. Specifically labeled formic acid-d, HCOOD, was also used to examine the core-excited fragmentation mechanisms. These deuterium-labeled experiments showed that HDO+ was formed via site-specific migration of a formyl hydrogen within an individual molecule, and that HD2O+ was produced via the subsequent transfer of a deuterium atom from the hydroxyl group of a nearest-neighbor molecule within a cationic cluster. Deuteron (proton) transfer from the hydroxyl site of a hydrogen-bond partner was also found to take place, producing deuteronated HCOOD.D+ (protonated HCOOH.H+) cations within the clusters.

Energy Band Structure of SiO2/4H-SiC Interfaces and its Modulation Induced by Intrinsic and Extrinsic Interface Charge Transfer

The energy band structure of SiO2/4H-SiC fabricated on (0001) Si- and (000-1) C-face substrates was investigated by means of synchrotron radiation x-ray photoelectron spectroscopy (SR-XPS). The band structure was found to be dependent on substrate orientation and oxide thickness due to both intrinsic and extrinsic effects that cause charge transfer at the SiO2/SiC interface. Our SR-XPS analysis revealed that the intrinsic conduction band offset of the SiO2/SiC for the C-face substrate is smaller than that for the Si-face. This means that, whereas C-face substrates exhibit high carrier mobility, a problem that is crucial to gate oxide reliability remains for SiC-based metal-oxide-semiconductor (MOS) devices owing to increased leakage current.

Study of the dissociation of nitrous oxide following resonant excitation of the nitrogen and oxygen K-shells.

A photochemistry study on nitrous oxide making use of site-selective excitation of terminal nitrogen, central nitrogen, and oxygen 1s-->3pi 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.

A High-resolution Study of Resonant Auger Decay Processes in N2O After Core Electron Excitation from Terminal Nitrogen, Central Nitrogen and Oxygen Atoms to the 3π LUMO

Decay spectra of N2O following excitation to the N terminal (Nt) → π*, N central (Nc) → π* and O is → π* intermediate states are reported. The final states reached after participator decay show res ...

Demonstration of up-conversion fluorescence from Ar clusters in intense free-electron-laser fields

Extreme ultraviolet (EUV) fluorescence emitted from Ar clusters irradiated by intense EUV free electron laser (FEL) pulses has been investigated. The EUV fluorescence spectra display rich structure at wavelengths shorter than the incident FEL wavelength of 51 nm. The results suggest that multiply-charged ions are produced following the ion-electron recombination processes which occur in the nanoplasma created by multi-photon excitation during the intense EUV-FEL pulses.

Long-lived, highly excited neutral hydrogen atom production following oxygen 1s photoexcitation of gas-phase water molecules

We have studied the production of long-lived, highly excited, neutral hydrogen atom fragments following oxygen 1s inner-shell excitation/ionization of gas-phase water molecules using synchrotron radiation. Striking differences to fragment ion and low-n neutral H yields are observed close to threshold. To investigate the decay pathways involved, the neutral fragments were also detected in coincidence with H+, O2 +, O+ and OH+ fragments.