S. L. Sorensen

Evidence for ultra-fast dissociation of molecular water from resonant Auger spectroscopy

We present direct evidence for ultra-fast dissociation of molecular water in connection photo-excitation of the Ols --> 4a(1) resonance. The core-excited H2O molecules are shown to dissociate into core-excited O*H and neutral H on a time scale comparable

Vibrational structure in the carbon 1s ionization of hydrocarbons: Calculation using electronic structure theory and the equivalent-cores approximation

A simple ab initio procedure is used to calculate the vibrational structure observed in the carbon 1s ionization of seven hydrocarbons (methane, deuteromethane, ethane, ethene, deuteroethene, ethyne, and deuteroethyne), with good agreement between experiment and theory. The method involves use of the equivalent-cores approximation, localized holes in molecules with equivalent carbons, and the harmonic oscillator approximation. The approach provides insight into the vibrational modes of the core-ionized molecules. It is potentially useful in extracting carbon 1s ionization energies from spectra from molecules having inequivalent carbons or in finding information on inner-hole lifetimes from inner-shell spectra.

The electronic structure of free water clusters probed by Auger electron spectroscopy

(H2O)(N) clusters generated in a supersonic expansion source with N approximately 1000 were core ionized by synchrotron radiation, giving rise to core-level photoelectron and Auger electron spectra (AES), free from charging effects. The AES is interpreted as being intermediate between the molecular and solid water spectra showing broadened bands as well as a significant shoulder at high kinetic energy. Qualitative considerations as well as ab initio calculations explain this shoulder to be due to delocalized final states in which the two valence holes are mostly located at different water molecules. The ab initio calculations show that valence hole configurations with both valence holes at the core-ionized water molecule are admixed to these final states and give rise to their intensity in the AES. Density-functional investigations of model systems for the doubly ionized final states--the water dimer and a 20-molecule water cluster--were performed to analyze the localization of the two valence holes in the electronic ground states. Whereas these holes are preferentially located at the same water molecule in the dimer, they are delocalized in the cluster showing a preference of the holes for surface molecules. The calculated double-ionization potential of the cluster (22.1 eV) is in reasonable agreement with the low-energy limit of the delocalized hole shoulder in the AES.

The vibrationally resolved C 1s core photoelectron spectra of methane and ethane

Recent progress in the development of high-resolution electron spectrometers in combination with highly monochromatized undulator radiation has allowed observation of the vibrationally resolved gas-phase C 1s photoelectron spectra of methane and ethane. For both molecules, the C–H stretching modes are well resolved and for ethane the active C–C stretching mode has been observed for the first time. The spectra have been measured at low kinetic energies and detailed fittings using post-collision interaction line profiles have been made both, using a free parameter fit and a fit adhering to a linear coupling model. The free parameter fit allows for any anharmonicity in the vibrational energies. The linear coupling model, on the other hand, assumes that the initial and final state potential curves are harmonic and differ only in the normal coordinates. This simple model is used to reduce the number of free parameters in the fit, which greatly simplifies the analysis. An intensity model based on the linear cou...

Observation of elastic scattering effects on photoelectron angular distributions in free Xe clusters

We report an observation of substantial deviations in the photoelectron angular distribution for photoionization of atoms in free Xe clusters compared to the case of photoionization of free atoms. The cross section, however, seems not to vary between the cluster and free atoms. This observation was made in the vicinity of the Xe 4d Cooper minimum, where the atomic angular distribution is known to vary dramatically. The angular distribution of electrons emitted from atoms in the clusters is more isotropic than that of free atoms over the entire kinetic energy range studied. Furthermore, the angular distribution is more isotropic for atoms in the interior of the clusters than for atoms at the surface. We attribute this deviation to elastic scattering of the outgoing photoelectrons. We have investigated two average cluster sizes, (N) approximate to 4000 and 1000 and found no significant differences between these two cases. (Less)

Bond-distance-dependent decay probability of the N 1s →π* core-excited state in N2

We report the observation of the unusually weak decay of the N 1s --> pi* core-excited N-2 molecule to the (B) over tilde (2)Sigma(u)(+) final state of N-2(+), which is only detectable in an exp ...

Core excitations of naphthalene: Vibrational structure versus chemical shifts

High-resolution x-ray photoelectron emission (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectra of naphthalene are analyzed in terms of the initial state chemical shifts and the vibrational fine structure of the excitations. Carbon atoms located at peripheral sites experience only a small chemical shift and exhibit rather similar charge-vibrational coupling, while the atoms in the bridging positions differ substantially. In the XPS spectra, C-H stretching modes provide important contributions to the overall shape of the spectrum. In contrast, the NEXAFS spectrum contains only vibrational progressions from particular C-C stretching modes. The accuracy of ab initio calculations of absolute electronic transition energies is discussed in the context of minute chemical shifts, the vibrational fine structure, and the state multiplicity.

Development of a four-element conical electron lens dedicated to high resolution Auger electron–ion(s) coincidence experiments

A four-element conical electron lens has been developed in view of its integration to a double toroidal electron energy analyzer (DTA) dedicated to Auger electron–ion coincidence measurements. The lens design, using electron trajectory numerical simulations, was entirely guided by the perspective of analyzing energetic electrons with high resolution in the multicoincidence regime. The design, construction, and experimental characterization stages of this electron optics system are described in this article. Emphasis is put on the importance of third generation synchrotron radiation sources when performing such multicoincidence experiments.

Femtosecond pump–probe photoelectron spectroscopy of predissociative Rydberg states in acetylene

We employ a pump–probe approach to molecular photoionization to study fast dissociation of Rydberg states in acetylene. By using time-resolved photoelectron spectroscopy to study the electronic state of the resulting ions we are able to monitor the system continuously during dissociation or rearrangement. We find that the predissociative lifetime for the 3R′′′ (v2′=1) Rydberg state is about 150 fs. We demonstrate a powerful new technique using time-correlated femtosecond harmonic generation and laser light pulses to study the time evolution of ultrafast dynamic processes in molecules.

VIBRATIONAL STRUCTURE OF THE CHLOROMETHANE SERIES, CH4-NCLN, STUDIED BY CORE PHOTOELECTRON SPECTROSCOPY AND AB INITIO CALCULATIONS

Vibrationally resolved C1s photoelectron spectra of the chloromethane series, CH4-nCln, are reported. The spectra are compared with results from ab initio calculations at the MP2 level using the Z+ ...