G. Prümper

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.

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.

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

Frustration of direct photoionization of Ar clusters in intense extreme ultraviolet pulses from a free electron laser

We have measured the kinetic energies of fragment ions from Ar clusters (average cluster size N~ 10?600) exposed to intense extreme ultraviolet free electron laser pulses (? ~ 61 nm, I~ 1.3? 1011 W cm?2). For small clusters (N 200), the average kinetic energy of ions strongly increases with increasing the cluster size, indicating a promotion of the multiple ionization, whereas the average kinetic energy is observed to be saturated for N 200. Considering how many photoelectrons can escape from the cluster, it was found that the size dependence of the ion kinetic energy exhibited the frustration of direct photoionization, which resulted from the strong Coulomb potential of the highly ionized cluster.

Ultrafast dissociation of F 1s excited SF6 probed by electron–ion momentum coincidence spectroscopy

Ultrafast dissociation of the SF6 molecule following F 1s → a*1g excitation has been studied by the coincident measurement of the kinetic energy of the resonantly emitted electron and the momentum of the fragment ion. The nuclear motion takes place on the same time scale as the Auger decay, leading to atomic-like F (1s)-Auger lines in the electron spectrum. De-tuning from the excitation resonance changes the ratio of the two time scales involved. We measured the shift of the atomic-like Auger line and the changes in the parameters that describe the corresponding ionic fragmentation dynamics as a function of the detuning energy. Our data are consistent with predictions based on electron spectroscopic measurements that resolved the Doppler-splitting of the Auger-line. We found that unlike in diatomic molecules a substantial fraction of the excitation energy remains in the neutral fragment(s).

Localization of inner-shell photoelectron emission and interatomic Coulombic decay in Ne2

We used cold target recoil ion momentum spectroscopy (COLTRIMS) to investigate the decay of Ne2 after K-shell photoionization. The breakup into Ne1+/Ne2+ shows interatomic Coulombic decay (ICD) occurring after a preceding atomic Auger decay. The molecular frame angular distributions of the photoelectron and the ICD electron show distinct, asymmetric features, which imply localization of the K-vacancy created at one of the two atomic sites of the Ne2 and an emission of the ICD electron from a localized site. The experimental results are supported by calculations in the frozen core Hartree–Fock approach.

Site-specific fragmentation caused by core-level photoionization in F3SiCH2CH2Si(CH3)3 vapor: Comparison between Si:1s and 2p photoionizations by means of photoelectron-photoion-photoion triple-coincidence spectroscopy

Site-specific fragmentation caused by Si:1s and 2p core-level photoionizations in F(3)SiCH(2)CH(2)Si(CH(3))(3) vapor was studied by energy-selected-photoelectron photoion-photoion triple-coincidence spectroscopy. The difference between the chemical shifts of the two Si sites is larger for the 1s ionization than for the 2p (2s) ionization. The fragmentation caused by the Si:1s ionization is more violent than that caused by the Si:2p ionization. The ions and ion pairs showing high site specificity for the Si:1s ionization belong to small fragments compared to those in the Si:2p ionization. Criteria for high site-specificity in fragmentation are discussed in conjunction with the present results.

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.

Multiple ionization of atomic argon irradiated by EUV free-electron laser pulses at 62 nm: evidence of sequential electron strip

We have investigated multiple ionization of atomic argon by extreme-ultraviolet light pulses (62 nm, 100 fs in width, <2 × 1014 W cm−2) at the free-electron laser facility in Japan, and observed highly charged ions with the charge state up to +6. The measured laser power dependence of the highly charged ions indicates that the multiple ionization proceeds via the sequential stripping of electrons.