Marc J. J. Vrakking

X-Ray Diffraction from Isolated and Strongly Aligned Gas-Phase Molecules with a Free-Electron Laser

We report experimental results on x-ray diffraction of quantum-state-selected and strongly aligned ensembles of the prototypical asymmetric rotor molecule 2,5-diiodobenzonitrile using the Linac Coherent Light Source. The experiments demonstrate first steps toward a new approach to diffractive imaging of distinct structures of individual, isolated gas-phase molecules. We confirm several key ingredients of single molecule diffraction experiments: the abilities to detect and count individual scattered x-ray photons in single shot diffraction data, to deliver state-selected, e.g., structural-isomer-selected, ensembles of molecules to the x-ray interaction volume, and to strongly align the scattering molecules. Our approach, using ultrashort x-ray pulses, is suitable to study ultrafast dynamics of isolated molecules.

Femtosecond wave‐packet dynamics studied by time‐resolved zero‐kinetic energy photoelectron spectroscopy

Femtosecond pump–probe zero‐kinetic‐energy (ZEKE) photoelectron spectroscopy is studied using the known wave‐packet dynamics of I2 (B state). The 340 fs wave‐packet period, wave‐packet dephasing and rephasing are observed in the ZEKE signal. The effect of various laser and ZEKE parameters on the wave‐packet dynamics is discussed.

Nonadiabatic wave packet dynamics: Experiment and theory in IBr

We present an experimental and a theoretical study of nonadiabatic wave packet dynamics in the intermediate coupling regime as exhibited by the IBr molecule. Using a femtosecond pump–probe molecular beam technique, we generated a wave packet which evolves on the electronically excited B 3Π0+/Y(0+) coupled states. The wave packet dynamics was detected by a time-delayed probe pulse which induced two photon ionization to the ground state of the IBr+ ion. The study consisted of a systematic variation of the pump laser wavelength from the crossing point of the two coupled states to the dissociation limit of the bound diabatic state. The theoretical study is based on the convolution of the products of the energy resolved X 1Σ+→B 3Π0+/Y(0+) bound–free dipole matrix elements and the free–bound two-photon ionization amplitudes (calculated exactly using the artificial channel method) with the profiles of the pump and probe pulses. The theoretical calculations reproduce the general decay, recurrence, and revivals ob...

Polarization gating and circularly-polarized high harmonic generation using plasmonic enhancement in metal nanostructures

We investigate possibilities to utilize field enhancement by specifically designed metal nanostructures for the generation of single attosecond pulses using the polarization gating technique. We predict the generation of isolated 59-attosecond-long pulses using 15-fs pump pulses with only a 0.6 TW/cm2 intensity. Our simulations also indicate the possibility to generate previously inaccessible high-harmonics with circular polarization by using an ensemble of vertically and horizontally orientated bow-tie structures. In the numerical simulation we used an extended Lewenstein model, which includes the spatial inhomogeneity in the hot spots and collisions of electrons with the metal surface.

High dynamic range bio-molecular ion microscopy with the Timepix detector.

Highly parallel, active pixel detectors enable novel detection capabilities for large biomolecules in time-of-flight (TOF) based mass spectrometry imaging (MSI). In this work, a 512 × 512 pixel, bare Timepix assembly combined with chevron microchannel plates (MCP) captures time-resolved images of several m/z species in a single measurement. Mass-resolved ion images from Timepix measurements of peptide and protein standards demonstrate the capability to return both mass-spectral and localization information of biologically relevant analytes from matrix-assisted laser desorption ionization (MALDI) on a commercial ion microscope. The use of a MCP-Timepix assembly delivers an increased dynamic range of several orders of magnitude. The Timepix returns defined mass spectra already at subsaturation MCP gains, which prolongs the MCP lifetime and allows the gain to be optimized for image quality. The Timepix peak resolution is only limited by the resolution of the in-pixel measurement clock. Oligomers of the protein ubiquitin were measured up to 78 kDa.

Attosecond Hole Migration in Benzene Molecules Surviving Nuclear Motion.

Hole migration is a fascinating process driven by electron correlation, in which purely electronic dynamics occur on a very short time scale in complex ionized molecules, prior to the onset of nuclear motion. However, it is expected that due to coupling to the nuclear dynamics, these oscillations will be rapidly damped and smeared out, which makes experimental observation of the hole migration process rather difficult. In this Letter, we demonstrate that the instantaneous ionization of benzene molecules initiates an ultrafast hole migration characterized by a periodic breathing of the hole density between the carbon ring and surrounding hydrogen atoms on a subfemtosecond time scale. We show that these oscillations survive the dephasing introduced by the nuclear motion for a long enough time to allow their observation. We argue that this offers an ideal benchmark for studying the influence of hole migration on molecular reactivity.

Field-free molecular alignment probed by the free electron laser in Hamburg (FLASH)

High flux extreme ultraviolet (XUV) sources like the free electron laser (FEL) in Hamburg (FLASH) offer the possibility of diffractive imaging of small objects. Irrespective of whether the diffraction is based on the detection of photons or photoelectrons, it is required that the measurement is done in the reference frame of the molecule meaning that, for a sample of several molecules, it is necessary to pre-align the molecules in the sample. As a step towards performing molecular frame diffraction experiments, we report experiments on field-free molecular alignment performed at FLASH. The impulsive alignment induced by a 100 fs near-infrared laser pulse in a rotationally cold CO2 sample is characterized by ionizing and dissociating the molecules with a time-delayed XUV-FEL pulse. The time-dependent angular distributions of ionic fragments measured by a velocity map imaging spectrometer exhibit rapid changes associated with the induced rotational dynamics. The experimental results show hints of a dissociation process that depends nonlinearly on the XUV intensity.

Velocity map imaging using an in-vacuum pixel detector.

The use of a new type in-vacuum pixel detector in velocity map imaging (VMI) is introduced. The Medipix2 and Timepix semiconductor pixel detectors (256 x 256 square pixels, 55 x 55 microm2) are well suited for charged particle detection. They offer high resolution, low noise, and high quantum efficiency. The Medipix2 chip allows double energy discrimination by offering a low and a high energy threshold. The Timepix detector allows to record the incidence time of a particle with a temporal resolution of 10 ns and a dynamic range of 160 micros. Results of the first time application of the Medipix2 detector to VMI are presented, investigating the quantum efficiency as well as the possibility to operate at increased background pressure in the vacuum chamber.

A semi-classical model of attosecond electron localization in dissociative ionization of hydrogen

In the development of attosecond molecular science, a series of experiments have recently been performed where ionic fragment asymmetries in the dissociative ionization of H(2) into H(+) + H and that of D(2) into D(+) + D were used to uncover electron localization processes that occur on the attosecond and few-femtosecond timescale. Electron localization was observed both in strong-field dissociative ionization using carrier envelope phase-stable few-cycle laser pulses [Kling et al., Science, 2006, 312, 246] and in a two-color extreme ultra-violet + infrared attosecond pump-probe experiment [Sansone et al., Nature, 2010, 465, 763]. Here we show that the observed electron localization can be well understood using a semi-classical model that describes the dynamics in terms of quasi-static states that take the interaction of the molecule with the laser field instantaneously into account. The electron localization is shown to be determined by the passage of the dissociating molecule through a regime where the laser-molecule interaction is neither diabatic nor adiabatic.

Carrier–envelope phase-tagged imaging of the controlled electron acceleration from SiO2 nanospheres in intense few-cycle laser fields

Waveform-controlled light fields offer the possibility of manipu- lating ultrafast electronic processes on sub-cycle timescales. The optical light- wave control of the collective electron motion in nanostructured materials is key to the design of electronic devices operating at up to petahertz frequencies. We have studied the directional control of the electron emission from 95nm 10 Authors to whom any correspondence should be addressed.