Fourfold Differential Photoelectron Circular Dichroism.

We report on a joint experimental and theoretical study of photoelectron circular dichroism (PECD) in methyloxirane. By detecting O 1s photoelectrons in coincidence with fragment ions, we deduce the molecule's orientation and photoelectron emission direction in the laboratory frame. Thereby, we retrieve a fourfold differential PECD clearly beyond 50%. This strong chiral asymmetry is reproduced by ab initio electronic structure calculations. Providing such a pronounced contrast makes PECD of fixed-in-space chiral molecules an even more sensitive tool for chiral recognition in the gas phase.

Photon-electron coincidence experiments at synchrotron radiation facilities with arbitrary bunch modes.

We report the adaptation of an electron-photon coincidence detection scheme to the multibunch hybrid mode of the synchrotron radiation source BESSY II (Helmholtz-Zentrum Berlin). Single-event-based data acquisition and evaluation, combined with the use of relative detection times between the coincident particles, enable the acquisition of proper coincidence signals from a quasi-continuous excitation pattern. The background signal produced by accidental coincidences in the time difference representation is modeled using the non-coincident electron and photon spectra. We validate the method by reproducing previously published results, which were obtained in the single bunch mode, and illustrate its usability for the multibunch hybrid mode by investigating the photoionization of CO2 into CO2 + B satellite states, followed by subsequent photon emission. The radiative lifetime obtained and the electron binding energy are in good agreement with earlier publications. We expect this method to be a useful tool to extend the versatility of coincident particle detection to arbitrary operation modes of synchrotron radiation facilities and other excitation sources without the need for additional experimental adjustments.

Determination of Mean Cluster Sizes by Fluorescence Detection upon Site-Specific Photoexcitation.

Electronic excitations in the valence shell of Ne clusters were studied by fluorescence spectroscopy. The measured fluorescence excitation functions contain information about the nature and number of excitonic states and the mean cluster size of the produced size distribution. Mean cluster sizes were determined by comparing surface and bulk contributions using a multidimensional fitting algorithm, with good agreement to commonly used scaling laws. The influence of different size distributions, which were not considered in previous investigations, on homogeneous noble gas cluster jets is implemented in the proposed model. The present work is the first approach using fluorescence spectroscopy for the determination of the mean size of Ne cluster jets created by supersonic expansion.

Setup for multicoincidence experiments of photons in the extreme ultraviolet to visible spectral range and charged particles-The solid angle maximization approach.

The coincident detection of particles is a powerful method in experimental physics, enabling the investigation of a variety of projectile-target interactions. The vast majority of coincidence experiments is performed with charged particles, as they can be guided by electric or magnetic fields to yield large detection probabilities. When a neutral species or a photon is one of the particles recorded in coincidence, its detection probability typically suffers from small solid angles. Here, we present two optical assemblies considerably enhancing the solid angle for photon detection in the extreme ultraviolet to visible spectral range. The efficiency and versatility of these assemblies are demonstrated for electron-photon coincidence detection, where electrons and photons emerge from fundamental processes after photoexcitation of gaseous samples by synchrotron radiation.

Recovery of High-Energy Photoelectron Circular Dichroism through Fano Interference.

It is commonly accepted that the magnitude of a photoelectron circular dichroism (PECD) is governed by the ability of an outgoing photoelectron wave packet to probe the chiral asymmetry of a molecule. To be able to accumulate this characteristic asymmetry while escaping the chiral ion, photoelectrons need to have relatively small kinetic energies of up to a few tens of electron volts. Here, we demonstrate a substantial PECD for very fast photoelectrons above 500 eV kinetic energy released from methyloxirane by a participator resonant Auger decay of its lowermost O 1s excitation. This effect emerges as a result of the Fano interference between the direct and resonant photoionization pathways, notwithstanding that their individual effects are negligibly small. The resulting dichroic parameter has an anomalous dispersion: It changes its sign across the resonance, which can be considered as an analogue of the Cotton effect in the x-ray regime.

NOVEL ANALYTICAL STUDY FOR REACTION INTERMEDIATES IN THE PRIMARY RADIATION INTERACTION OF DNA USING A SYNCHROTRON RADIATION-INDUCED LUMINESCENCE SPECTROSCOPY.

To identify the precise molecular processes to induce DNA lesions, we attempt a novel spectroscopy of X-ray induced luminescence (XIL) using soft X-ray synchrotron radiation, which is a non-destructive analysis of the reaction intermediates in the elementary reaction pathway of damage induction and self-organized restoration. Using a liquid micro-jet technique to introduce aqueous samples in a vacuum chamber, we measure UV-visible luminescence from nucleotide solution as a function of the soft X-ray energy from the nitrogen to oxygen K-edge region. The XIL intensities for the nucleotide solutions are significantly enhanced in the soft X-ray region (410-530 eV) which is ascribed to the K-shell excitation/ionization of nitrogen atoms in the nucleobases. Furthermore, the XIL spectra do not show any signature of X-ray absorption near-edge structure (XANES) of the nucleobases. This is because the luminescence intensities collected from the integral area of the micro-jet only reflect the quantum yield of luminescence of the absorbed X-ray into UV-visible light irrespective of the absorption cross sections, i.e. of XANES. Thus the present result is the first evidence of luminescence as a result of X-ray absorption of aqueous nucleotides.

Magnetic properties of artificially designed magnetic stray field landscapes in laterally confined exchange-bias layers.

Magnetic stray fields generated by domain walls (DWs) have attracted significant attention as they might be employed for precise positioning and active control of micro- and nano-sized magnetic objects in fluids or in the field of magnonics. The presented work intends to investigate the near-field response of magnetic stray field landscapes above generic types of charged DWs as occurring in thin films with in-plane anisotropy and preferential formation of Néel type DWs when disturbed by external magnetic fields. For this purpose, artificial magnetic stripe domain patterns with three defined domain configurations, i.e. head-to-head (tail-to-tail), head-to-side, and side-by-side, were fabricated via ion bombardment induced magnetic patterning of an exchange-biased IrMn/CoFe bilayer. The magnetic stray field landscapes as well as the local magnetization reversal of the various domain configurations were analyzed in an external magnetic field by scanning magnetoresistive microscopy and compared to micromagnetic simulations.

Angle-Resolved Auger Spectroscopy as a Sensitive Access to Vibronic Coupling.

In the angle-averaged excitation and decay spectra of molecules, vibronic coupling may induce the usually weak dipole-forbidden transitions by the excitation intensity borrowing mechanism. The present complementary theoretical and experimental study of the resonant Auger decay of core-to-Rydberg excited CH_{4} and Ne demonstrates that vibronic coupling plays a decisive role in the formation of the angle-resolved spectra by additionally involving the decay rate borrowing mechanism. Thereby, we propose that the angle-resolved Auger spectroscopy can in general provide very insightful information on the strength of the vibronic coupling.

Angular momentum sensitive two-center interference.

In quantum mechanics the Young-type double-slit experiment can be performed with electrons either traveling through a double slit or being coherently emitted from two inversion symmetric molecular sites. In the latter one the valence photoionization cross sections of homonuclear diatomic molecules were predicted to oscillate over kinetic energy almost 50 years ago. Beyond the direct proof of the oscillatory behavior of these photoionization cross sections σ, we show that the angular distribution of the emitted electrons reveals hitherto unexplored information on the relative phase shift between the corresponding partial waves through two-center interference patterns.

The J = 2 ortho levels of the v = 0 to 6 np singlet Rydberg series of molecular hydrogen revisited.

The energies of the J = 2 ortho levels of the v = 0 to 6 Rydberg np singlet series of molecular hydrogen with absolute intensities of the R(1) and P(3) absorption lines were measured by a high-resolution synchrotron radiation experiment and calculated through a full ab initio multi-channel quantum defect approach.

The J = 1 para levels of the v = 0 to 6 np singlet Rydberg series of molecular hydrogen revisited.

The energies and the widths of the J = 1 para levels of the v = 0 to 6 Rydberg np singlet series of molecular hydrogen with absolute intensities of the R(0) and P(2) absorption lines were measured by a high - resolution synchrotron radiation experiment and calculated through a full ab initio multichannel quantum defect theory approach. On the basis of the agreement between theory and experiment, 31 levels were either reassigned or assigned for the first time.

The transition probabilities from the ground state to the excited J = 0 1Σu(+) levels of H2: measurements and ab initio quantum defect study.

The energies, widths and absolute intensities of the P(1) v'' = 0, J'' = 1 absorption transitions of H(2) have been measured in the spectral range of 81-75 nm using monochromatized synchrotron radiation. This work completes and extends previous observations, in particular those of Herzberg and Jungen [J. Mol. Spectrosc. 41, 425 (1972)]. Ab initio multichannel quantum defect theory (MQDT) is used to corroborate the spectral analysis of the experimental data. Line intensities and decay widths are also calculated using MQDT.

Single center method: a computational tool for ionization and electronic excitation studies of molecules.

We discuss the recent progress in the development of the single center (SC) method for computation of highly-delocalized discrete and partial photoelectron wave continuous functions of molecules. Basic equations of the SC method are presented, and an efficient scheme for the numerical solution of a system of coupled Hartree-Fock equations for a photoelectron is described. Several illustrative applications of the method to photoionization and electronic excitation processes in diatomic molecules are considered. Thereby, we demonstrate its potential for theoretically studying angularly resolved molecular photoionization processes.

Synchrotron vacuum ultraviolet radiation studies of the D (1)Π(u) state of H(2).

The 3pπD (1)Π(u) state of the H(2) molecule was reinvestigated with different techniques at two synchrotron installations. The Fourier transform spectrometer in the vacuum ultraviolet wavelength range of the DESIRS beamline at the SOLEIL synchrotron was used for recording absorption spectra of the D (1)Π(u) state at high resolution and high absolute accuracy, limited only by the Doppler contribution at 100 K. From these measurements, line positions were extracted, in particular, for the narrow resonances involving (1)Π(u) (-) states, with an accuracy estimated at 0.06 cm(-1). The new data also closely match multichannel quantum defect calculations performed for the Π(-) components observed via the narrow Q-lines. The Λ-doubling in the D (1)Π(u) state was determined up to v=17. The 10 m normal incidence scanning monochromator at the beamline U125/2 of the BESSY II synchrotron, combined with a home-built target chamber and equipped with a variety of detectors, was used to unravel information on ionization, dissociation, and intramolecular fluorescence decay for the D (1)Π(u) vibrational series. The combined results yield accurate information on the characteristic Beutler-Fano profiles associated with the strongly predissociated Π(u) (+) parity components of the D (1)Π(u) levels. Values for the parameters describing the predissociation width as well as the Fano-q line shape parameters for the J=1 and J=2 rotational states were determined for the sequence of vibrational quantum numbers up to v=17.

Symmetry-forbidden electronic state interference observed in angularly resolved NO+ (A 1Π) deexcitation spectra of the N*O(2σ(-1)2π(2)) resonance.

Quantum mechanical interference between different pathways in inner-shell resonance excitation-deexcitation spectra is a realization of a double-slit experiment on the atomic scale. If the intermediate inner-shell resonances are of different symmetries, this interference is symmetry forbidden in the solid-angle-averaged or magic-angle-recorded deexcitation spectra. It has, however, been suggested that interference may by observable in off-magic-angle-recorded spectra. Here, we prove this interference in angularly resolved deexcitation spectra of the 2σ(-1)2π(2)(2Δ,2Σ±) resonances of N*O by a quantitative comparison between ab initio calculations and experiment.

Domain-wall movement control in Co/Au multilayers by He(+)-ion-bombardment-induced lateral coercivity gradients.

Defined perpendicular anisotropy gradients in the Co sublayers of a [Co(0.6 nm)/Au(2 nm)](3) sputter-deposited multilayer have been introduced by light ion bombardment through a wedged Au stopper layer. Within such a layer system, domain walls between up- and down-magnetized areas are controllably movable by an external perpendicular homogeneous magnetic field. This method and layer system is very promising for a controlled magnetic particle transport within the stray fields of the moving domain walls.

Neutral dissociation of the I, I', and I" vibronic progressions of O2.

It is suggested that the main mechanism for neutral dissociation of the I, I('), and I(") vibronic progressions in O(2) is due to their interaction with the vibrational continuum of the 1pi(u) (-1)(A (2)Pi(u))3ssigma(g) (3)Pi(u)(v(epsilon)) Rydberg state (J state) leading to the formation of the O(2p(4) (3)P)+O( *)(2p(3)((4)S)3s (3)S) fragments. In order to justify this, the O I 2p(3)((4)S)3s (3)S-->2p(4) (3)P fluorescence emission cross section following the neutral dissociation of the O(2) 1pi(u) (-1)(a (4)Pi(u))4ssigma(g)/3ddelta(g)/3dsigma(g) (3)Pi(u)(v) Rydberg states is simulated in the exciting-photon energy range of 14.636-16.105 eV. The results of high-resolution measurements (H. Liebel et al., J. Phys. B 34, 2581 (2001)) can be reproduced if a small adjustment of the computed potential curve of the J state is applied. Non-Franck-Condon resonant intensity distributions of the I, I('), and I(") progressions observed in the experiment are qualitatively explained by the presence of the O(2) 1pi(g) (-1)(X (2)Pi(g))npsigma(u)/nfsigma(u)/nfdelta(u) (3)Pi(u) perturber states. Present calculations allow to decide between two different assignments of the I, I('), and I(") states available in literature.

H2 superexcited states: experimental and theoretical characterization of their competing decay-channel fluorescence, dissociation, and ionization.

The absolute cross sections for the competing decay channels fluorescence, dissociation, and ionization of photoexcited long-lived superexcited H(2) molecular levels have been measured from the ionization threshold of H(2) up to the H(1s)+H(n=3) dissociation limit. The total and partial natural widths of these levels have been determined. Good agreement is found with first principles calculations carried out by multichannel quantum defect theory. The calculations reproduce the balance between the competing decay processes as well as its substantial level-to-level evolution.

The study of the D(') (1)Pi(u) state of H(2): transition probabilities from the ground state, predissociation yields, and natural linewidths.

The absorption spectrum of the H(2) molecule was studied at high resolution in the 81-72 nm spectral range. A detailed analysis of the D(') (1)Pi(u)-->X (1)Sigma(g) (+) electronic band system is reported. In the spectrum, more than 70 new lines were assigned. For wavelengths longer than 75 nm, the D(') (1)Pi(u) (+) and (1)Pi(u) (-) components show a clearly different behavior: Tauhe (1)Pi(u) (+) one dissociates into H(1s)+H(n=2) whereas the (1)Pi(u) (-) one leads to molecular fluorescence. For shorter wavelengths, both components are predissociated into H(1s)+H(n=3). The predissociation yields, the dissociation widths, and the absolute values of the transition probabilities were measured over the vibrational progression from v(')=3 to 17, i.e., up to the dissociation limit. The comparison between these absolute transition probabilities and the values calculated in the adiabatic and nonadiabatic approximations demonstrates clearly the importance of nonadiabatic couplings.

Study of the B"B 1Sigmau+ state of H2: transition probabilities from the ground state, dissociative widths, and Fano parameters.

The transition probabilities, the dissociation widths, and the associated Fano parameters for rovibronic lines with J"=0,...,3 of the absorption bands of the B"B 1Sigmau+ state out of the X 1Sigmag+ v"=0 ground state were measured over the complete vibrational progression, showing clearly that only the inner-well state with B" 4psigma character can absorb vuv light and predissociate efficiently. The absolute values of these transition probablities, predissociation widths, and Fano parameters were found to agree well with ab initio calculations if one takes into account that the calculations neglect nonadiabatic couplings.