Toralf Lischke

Isotope-induced partial localization of core electrons in the homonuclear molecule N2

Because of inversion symmetry and particle exchange, all constituents of homonuclear diatomic molecules are in a quantum mechanically non-local coherent state; this includes the nuclei and deep-lying core electrons. Hence, the molecular photoemission can be regarded as a natural double-slit experiment: coherent electron emission originates from two identical sites, and should give rise to characteristic interference patterns. However, the quantum coherence is obscured if the two possible symmetry states of the electronic wavefunction (‘gerade’ and ‘ungerade’) are degenerate; the sum of the two exactly resembles the distinguishable, incoherent emission from two localized core sites. Here we observe the coherence of core electrons in N2 through a direct measurement of the interference exhibited in their emission. We also explore the gradual transition to a symmetry-broken system of localized electrons by comparing different isotope-substituted species—a phenomenon analogous to the acquisition of partial ‘which-way’ information in macroscopic double-slit experiments.

Valence ionization of water clusters: from isolated molecules to bulk.

The valence photoelectron spectra of water clusters are studied experimentally and by ab initio calculations. The size dependence of the vertical ionization energy of the outermost orbitals is explicitly shown. A shift toward lower values is observed. For small cluster sizes, it can be rationalized as an effect of charge delocalization as the system is becoming more extended. Ionization energies of larger clusters decrease linearly with inverse cluster radius and asymptotically approach the value of liquid water. In the calculations, we apply a reflection principle approach based on sampling a quantum mechanical distribution of different initial-state geometries to clusters. An excellent agreement of peak shapes calculated thus with measured ones is shown. Using additional polarization fields, the extension of this approach to the photoionization of liquid water is demonstrated. Upon deuteration of the water clusters, we experimentally and theoretically find slightly larger absolute values of the vertical ionization energies. We suggest that the measurement of electron ionization energies can be used as an alternative means to characterize water cluster sizes, which can complement the use of scaling laws.

Photoelectron circular dichroism in core level ionization of randomly oriented pure enantiomers of the chiral molecule camphor

The inner-shell photoionization of unoriented camphor molecules by circularly polarized light has been investigated from threshold to a photoelectron kinetic energy of approximately 65 eV. Photoelectron spectra of the carbonyl C 1s orbital, recorded at the magic angle of 54.7 degrees with respect to the light propagation direction, show an asymmetry of up to 6% on change of either the photon helicity or molecular enantiomer. These observations reveal a circular dichroism in the angle resolved emission with an asymmetry between forward and backward scattering (i.e., 0 degrees and 180 degrees to the light beam) which can exceed 12%. Since the initial state is an atomiclike spherically symmetric orbital, this strongly suggests that the asymmetry is caused by final-state effects dependent on the chiral geometry of the molecule. These findings are confirmed by electron multiple scattering calculations of the photoionization dynamics in the electric-dipole approximation.

Young's double-slit experiment using core-level photoemission from N2: revisiting Cohen–Fano's two-centre interference phenomenon

The core-level photoelectron spectra of N2 molecules are observed at high energy resolution, resolving the 1σg and 1σu components as well as the vibrational components in the extended energy region from the threshold up to 1 keV. The σg/σu cross section ratios display modulation as a function of photoelectron momentum due to the two-centre interference, analogous to the classical Young’s double-slit experiment, as predicted by Cohen and Fano a long time ago. The Cohen–Fano interference modulations display different phases depending on the vibrational excitations in the core-ionized state. Extensive ab initio calculations have been performed within the Hartree–Fock and random phase approximations in prolate spheroidal coordinates. The dependence of photoionization amplitudes on the vibrational states was taken into account using the Born–Oppenheimer approximation. The ab initio results are in reasonable agreement with the experimental data. The theoretical analysis allows the modulation to be connected with the onset of transitions to the states of increasing orbital angular momentum which occurs at increasing photon energies. Deviation from the Cohen–Fano formula is found for both the experimental and the ab initio results and is attributed to electron scattering by the neighbouring atom. A new formula for the interference modulation is derived within the framework of the multiple scattering technique. It differs from the classical Cohen–Fano formula by the addition of twice the scattering phase of the photoelectron by the neighbouring atom. We demonstrate that

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.

Double-slit experiment with a polyatomic molecule: vibrationally resolved C 1s photoelectron spectra of acetylene

We report the first evidence for double-slit interferences in a polyatomic molecule, which we have observed in the experimental carbon 1s photoelectron spectra of acetylene (or ethyne). The spectra have been measured over the photon energy range of 310-930eV and show prominent oscillations in the intensity ratios g()/ u() for the vibrational quantum numbers = 0,1 and for the ratios s( = 1)/ s( = 0) for the symmetry s = g,u. The experimental findings are in very good agreement with ab initio density

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.

Performance of a short "magnetic bottle" electron spectrometer.

In this article, a newly constructed electron spectrometer of the magnetic bottle type is described. The instrument is part of an apparatus for measuring the electron spectra of free clusters using synchrotron radiation. Argon and helium outer valence photoelectron spectra have been recorded in order to investigate the characteristic features of the spectrometer. The energy resolution (E/ΔE) has been found to be ∼30. Using electrostatic retardation of the electrons, it can be increased to at least 110. The transmission as a function of kinetic energy is flat, and is not impaired much by retardation with up to 80% of the initial kinetic energy. We have measured a detection efficiency of most probably 0.6(-0.1) (+0.05), but at least of 0.4. Results from testing the alignment of the magnet, and from trajectory simulations, are also discussed.

Valence and C 1s core level photoelectron spectra of camphor

Abstract The valence photoelectron spectrum of camphor has been recorded with 95 eV synchrotron radiation, with better definition than previous He I spectra. The spectrum is interpreted by comparison with these He I results and with the aid of an outer-valence Green’s Function calculation of the orbital ionization energies. These calculations closely reproduce the observed vertical ionization energies in the outer valence region. A core level spectrum of the C 1s region ( h ν=357.9 eV) is also presented and reveals a marked shift of the carbonyl carbon relative to all others in the molecule.

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.