T. Laarmann

Multiple ionization of atom clusters by intense soft X-rays from a free-electron laser

Intense radiation from lasers has opened up many new areas of research in physics and chemistry, and has revolutionized optical technology. So far, most work in the field of nonlinear processes has been restricted to infrared, visible and ultraviolet light, although progress in the development of X-ray lasers has been made recently. With the advent of a free-electron laser in the soft-X-ray regime below 100 nm wavelength, a new light source is now available for experiments with intense, short-wavelength radiation that could be used to obtain deeper insights into the structure of matter. Other free-electron sources with even shorter wavelengths are planned for the future. Here we present initial results from a study of the interaction of soft X-ray radiation, generated by a free-electron laser, with Xe atoms and clusters. We find that, whereas Xe atoms become only singly ionized by the absorption of single photons, absorption in clusters is strongly enhanced. On average, each atom in large clusters absorbs up to 400 eV, corresponding to 30 photons. We suggest that the clusters are heated up and electrons are emitted after acquiring sufficient energy. The clusters finally disintegrate completely by Coulomb explosion.

Shell explosion and core expansion of xenon clusters irradiated with intense femtosecond soft x-ray pulses

The disintegration mechanisms for xenon clusters in intense femtosecond soft x-ray pulses from the FLASH free electron laser are investigated. The clusters are irradiated at a wavelength of ? = 13.7 nm (h? = 90.5 eV) and power densities of 5 ? 1014 W cm?2. During the 10 fs pulse the Xe clusters are transformed into a highly excited, multiply charged nanoplasma. Simulating the ion kinetic energies in an electrostatic model suggests that highly charged ions explode off the surface due to Coulomb repulsion while the inner core expands in a hydrodynamic expansion. The current results yield evidence for efficient ionization of the clusters in addition to direct multistep photoemission.

Charge recombination in soft x-ray laser produced nanoplasmas

The ionization and charge separation processes of nanoplasmas created by resonant excitation of atomic clusters in intense soft x-ray pulses have been investigated. Through irradiation with femtosecond pulses from the FLASH free electron laser (FEL) at ? = 13.7 nm and power densities exceeding 1014 W cm?2 the clusters are highly ionized with transient atomic charge states up to 9+. Variation of the cluster composition from pristine to doped and core?shell systems allows tracking of the spatial origin and charge states of the fragments yielding insight into the nanoplasma dynamics. The data give evidence for efficient charge redistribution processes leading to a Coulomb explosion of the cluster outer part and recombination of the nanoplasma core. The experiments show qualitatively different processes for (soft) x-ray produced nanoplasmas from the optical (IR) strong-field regime where the clusters disintegrate completely in a Coulomb explosion.

The electronically excited states of helium clusters: an unusual example for the presence of Rydberg states in condensed matter

The nature of the electronically excited states of He clusters and their relaxation mechanisms are investigated by spectroscopy using monochromatized synchrotron radiation. Time correlated fluorescence excitation and energy resolved luminescence spectra of the clusters are recorded in separate wavelength ranges. The size of the clusters and the isotopic constitution is also varied. The spectral features are analysed and discussed particularly with regard to the high lying states and their possible Rydberg nature. While Rydberg states seem not to exist in the interior region of large clusters there is experimental evidence that sharp lines in the spectrum are either due to He Rydberg atoms or excimer molecules in high vibrational states bound at the surface of large clusters or due to very small positively charged clusters with the Rydberg electron outside. The spectra of large 3He clusters exhibit a larger contribution of Rydberg lines than 4He clusters. He clusters also emit fluorescence at energies above the ionization energy of He atoms. This is attributed to the barrier for the injection of electrons into the conduction band which was found to be 1.35 eV for 4He and 0.95 eV for 3He clusters, respectively.

Ultrafast excitation, ionization, and fragmentation of C60

Publisher Summary This chapter presents notions, facts, and findings on C60 and the fullerenes. The chapter discusses basic terminology and concepts from the area of atoms and molecules in strong fields. Some experimental aspects of studying molecules in intense, short pulse laser fields are addressed. The chapter also explains the ionization process, charge states, and fragmentation after short pulse laser interaction with C60 as observed by mass spectroscopy. The intensity dependence of these processes and compares saturation intensities for the ionization processes with simple atomic systems is addressed in the chapter. Further, the above threshold ionization (ATI) observed in photoelectron spectra at various short pulse laser intensities are discussed and compared with the recent theoretical results. Theoretical comparison leads to a critical discussion of the primary excitation mechanism in an intense laser pulse. The chapter also discusses the band structure model in condensed matter, that is, for a semiconductor in the case of C60. The chapter illustrates this with an example: the non-resonant excitation of Rydberg states in C60. Further, the fast fragmentation processes of C60 beyond the established statistical fragmentation processes known to occur on the ns to μs time scale are addressed.

Femtosecond pulse shaping as analytic tool in mass spectrometry of complex polyatomic systems

An additional dimension to mass spectrometric studies on building blocks of proteins is discussed in this paper. The present approach is based on tailored femtosecond laser pulses, using the concept of strong-field pulse shaping in an adaptive feedback loop. We show that control strategies making use of coherent properties of the electromagnetic wave allow one to break pre-selected backbone bonds in amino acid complexes that may be regarded as peptide model systems. Studies on different chromophores, such as phenylalanine and alanine, while keeping the backbone structure unchanged elucidates the effect of the excitation dynamics on the relaxation pathways. The observation of protonated species in the corresponding mass spectra indicates that optimal control of ultrafast laser pulses may even be useful to study intramolecular reactions such as hydrogen- or proton-transfer in particular cases. This opens new perspectives for biophysical and biochemical research, since these photochemical reactions are suggested to explain, e.g. photostability of DNA.

C60 in intense short pulse laser fields down to 9fs: Excitation on time scales below e-e and e-phonon coupling

The interaction of C60 fullerenes with 765-797 nm laser pulses as short as 9 fs at intensities of up to 3.7 x 10(14) W cm(-2) is investigated with photoion spectroscopy. The excitation time thus addressed lies well below the characteristic time scales for electron-electron and electron-phonon couplings. Thus, energy deposition into the system is separated from energy redistribution among the various electronic and nuclear degrees of freedom. Insight into fundamental photoinduced processes such as ionization and fragmentation is obtained from the analysis of the resulting mass spectra as a function of pulse duration, laser intensity, and time delay between pump and probe pulses, the latter revealing a memory effect for storing electronic energy in the system with a relaxation time of about 50 fs. Saturation intensities and relative abundances of (multiply charged) parent and fragment ions (C60(q+), q=1-6) are fingerprints for the ionization and fragmentation mechanisms. The observations indicate that for final charge states q>1 the well known C60 giant plasmon resonance is involved in creating ions and a significant amount of large fragments even with 9 fs pulses through a nonadiabatic multielectron dynamics. In contrast, for energetic reasons singly charged ions are generated by an essentially adiabatic single active electron mechanism and negligible fragmentation is found when 9 fs pulses are used. These findings promise to unravel a long standing puzzle in understanding C60 mass spectra generated by intense femtosecond laser pulses.

Size and isotope effects of helium clusters and droplets: identification of surface and bulk-volume excitations

We report a comprehensive investigation of the electronically excited states of helium clusters and droplets of sizes ranging from a few to several 10(7) atoms using time-resolved fluorescence excitation spectroscopy and quantum chemical ab initio calculations. We employ various approaches for our analysis considering the lifetime-dependence of the fluorescence intensity, spectral shifts, intensity scaling with cluster size, isotopic dependence, and density-dependence of the calculated electron wave function radii. A unique feature of helium clusters and droplets is their radially varying particle density. Our results show that short-lived fluorescence is sensitive to regions of increased density and probes excitations located in the bulk volume, whereas long-lived fluorescence is sensitive to regions of reduced density such as for small clusters or for the surface of large droplets. Spectra of (3)He droplets serve as a reference for low density, but are free from contributions of small clusters. This allows us to distinguish regions of reduced density as these can be due to both surface states or small clusters. Our analysis reveals a picture where spectral features are related to regions of different density due to isotopic composition, cluster size, and surface or bulk volume location of the excitations. The 2s and 2p related excitations appear as blue-shifted wings for small clusters or for excited atoms within the surface layer, whereas in the bulk-volume of large droplets, they appear as distinct bands with large intensities, dominating the entire spectrum. Excitations at energies higher than 23 eV are unambiguously assigned to regions of low and medium density location within the deeper parts of the surface layer but show no relation to the bulk volume. Our findings support the idea that in liquid helium high-lying states and, in particular, Rydberg states are quenched in favor of the 2s and 2p excitations.

Fragmentation dynamics of fullerenes in intense femtosecond-laser fields: Loss of small neutral fragments on a picosecond time scale

The fragmentation dynamics of C60 irradiated with intense femtosecond laser pulses is studied with one-color pump-probe spectroscopy. Small neutral fragments (C, C2, and C3) are formed by an 800-nm pump pulse which are then postionized by a delayed probe pulse. The respective ion signals detected by the time-of-flight mass spectrometry dramatically increase on a time scale of 10-20 ps.

A time resolved VUV fluorescence study of hydrogen clusters: evidence of a liquid phase

Abstract The mobility of Xe atoms captured from a cross jet by hydrogen clusters is investigated with time resolved VUV fluorescence excitation spectroscopy. A band blue shifted by 0.5 eV with respect to the 5p→6s transition of free Xe atoms is observed. It is attributed to Xe atoms profoundly embedded in hydrogen clusters and surrounded by several layers of hydrogen. The complete absence of features related to surface sites gives evidence that after the pick up process the xenon atoms penetrate deep into the interior of the hydrogen clusters. This indicates that hydrogen clusters show a liquid-like behavior similar to helium clusters, though their estimated temperature (∼6 K) is much below the triple point of hydrogen (14 K).