Melanie Mucke

Ultrafast X-ray Auger probing of photoexcited molecular dynamics

Molecules can efficiently and selectively convert light energy into other degrees of freedom. Disentangling the underlying ultrafast motion of electrons and nuclei of the photoexcited molecule presents a challenge to current spectroscopic approaches. Here we explore the photoexcited dynamics of molecules by an interaction with an ultrafast X-ray pulse creating a highly localized core hole that decays via Auger emission. We discover that the Auger spectrum as a function of photoexcitation--X-ray-probe delay contains valuable information about the nuclear and electronic degrees of freedom from an element-specific point of view. For the nucleobase thymine, the oxygen Auger spectrum shifts towards high kinetic energies, resulting from a particular C-O bond stretch in the ππ* photoexcited state. A subsequent shift of the Auger spectrum towards lower kinetic energies displays the electronic relaxation of the initial photoexcited state within 200 fs. Ab-initio simulations reinforce our interpretation and indicate an electronic decay to the nπ* state.

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.

Using covariance mapping to investigate the dynamics of multi-photon ionization processes of Ne atoms exposed to X-FEL pulses

We report on a detailed investigation into the electron emission processes of Ne atoms exposed to intense femtosecond x-ray pulses, provided by the Linac Coherent Light Source Free Electron Laser (FEL) at Stanford. The covariance mapping technique is applied to analyse the data, and the capability of this approach to disentangle both linear and nonlinear correlation features which may be hidden on coincidence maps of the same data set is demonstrated. Different correction techniques which enable improvements on the quality of the spectral features extracted from the covariance maps are explored. Finally, a method for deriving characteristics of the x-ray FEL pulses based on covariance mapping in combination with model simulations is presented.

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.

Covariance mapping of two-photon double core hole states in C2H2 and C2H6 produced by an x-ray free electron laser

Few-photon ionization and relaxation processes in acetylene (C2H2) and ethane (C2H6) were investigated at the linac coherent light source x-ray free electron laser (FEL) at SLAC, Stanford using a highly efficient multi-particle correlation spectroscopy technique based on a magnetic bottle. The analysis method of covariance mapping has been applied and enhanced, allowing us to identify electron pairs associated with double core hole (DCH) production and competing multiple ionization processes including Auger decay sequences. The experimental technique and the analysis procedure are discussed in the light of earlier investigations of DCH studies carried out at the same FEL and at third generation synchrotron radiation sources. In particular, we demonstrate the capability of the covariance mapping technique to disentangle the formation of molecular DCH states which is barely feasible with conventional electron spectroscopy methods.

Probing ultrafast ππ* / nπ* internal conversion in organic chromophores via K-edge resonant absorption

Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrum at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. High-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.Many photo-induced processes such as photosynthesis occur in organic molecules, but their femtosecond excited-state dynamics are difficult to track. Here, the authors exploit the element and site selectivity of soft X-ray absorption to sensitively follow the ultrafast ππ*/nπ* electronic relaxation of hetero-organic molecules.

The photoelectron angular distribution of water clusters

The angular distribution of photoelectrons emitted from water clusters has been measured by linearly polarized synchrotron radiation of 40 and 60 eV photon energy. Results are given for the three outermost valence orbitals. The emission patterns are found more isotropic than for isolated molecules. While a simple scattering model is able to explain most of the deviation from molecular behavior, some of our data also suggest an intrinsic change of the angular distribution parameter. The angular distribution function was mapped by rotating the axis of linear polarization of the synchrotron radiation.

Interatomic Coulombic decay in mixed NeKr clusters

We report the occurrence of interatomic Coulombic decay (ICD) in mixed NeKr clusters. A well-defined feature ranging from 9 to 12 eV in kinetic energy is observed in coincidence with the Ne 2s photoelectrons. It derives from an ICD process, in which an initial Ne 2s vacancy is filled by a Ne 2p electron and an electron is emitted from a 4p level on a neighboring Kr atom. We have studied the dependence of the effect on photon energy, cluster composition, and cluster size. Interestingly, the ICD electron energy increases slightly and grows a shoulder on going from 2% to 5% Kr in the coexpansion process, which we interpret in terms of surface versus bulk effects.

Auger electron and photoabsorption spectra of glycine in the vicinity of the oxygen K-edge measured with an X-FEL

We report the first measurement of the near oxygen K-edge auger spectrum of the glycine molecule. Our work employed an x-ray free electron laser as the photon source operated with input photon energies tunable between 527 and 547 eV. Complete electron spectra were recorded at each photon energy in the tuning range, revealing resonant and non-resonant auger structures. Finally ab initio theoretical predictions are compared with the measured above the edge auger spectrum and an assignment of auger decay channels is performed.

Disentangling formation of multiple-core holes in aminophenol molecules exposed to bright X-FEL radiation

Competing multi-photon ionization processes, some leading to the formation of double core hole states, have been examined in 4-aminophenol. The experiments used the linac coherent light source (LCLS) x-ray free electron laser, in combination with a time-of-flight magnetic bottle electron spectrometer and the correlation analysis method of covariance mapping. The results imply that 4-aminophenol molecules exposed to the focused x-ray pulses of the LCLS sequentially absorb more than two x-ray photons, resulting in the formation of multiple core holes as well as in the sequential removal of photoelectrons and Auger electrons (so-called PAPA sequences).