F. Lépine

Electron localization following attosecond molecular photoionization

For the past several decades, we have been able to directly probe the motion of atoms that is associated with chemical transformations and which occurs on the femtosecond (10−15-s) timescale. However, studying the inner workings of atoms and molecules on the electronic timescale has become possible only with the recent development of isolated attosecond (10−18-s) laser pulses. Such pulses have been used to investigate atomic photoexcitation and photoionization and electron dynamics in solids, and in molecules could help explore the prompt charge redistribution and localization that accompany photoexcitation processes. In recent work, the dissociative ionization of H2 and D2 was monitored on femtosecond timescales and controlled using few-cycle near-infrared laser pulses. Here we report a molecular attosecond pump–probe experiment based on that work: H2 and D2 are dissociatively ionized by a sequence comprising an isolated attosecond ultraviolet pulse and an intense few-cycle infrared pulse, and a localization of the electronic charge distribution within the molecule is measured that depends—with attosecond time resolution—on the delay between the pump and probe pulses. The localization occurs by means of two mechanisms, where the infrared laser influences the photoionization or the dissociation of the molecular ion. In the first case, charge localization arises from quantum mechanical interference involving autoionizing states and the laser-altered wavefunction of the departing electron. In the second case, charge localization arises owing to laser-driven population transfer between different electronic states of the molecular ion. These results establish attosecond pump–probe strategies as a powerful tool for investigating the complex molecular dynamics that result from the coupling between electronic and nuclear motions beyond the usual Born–Oppenheimer approximation.

Time-Resolved Holography with Photoelectrons

The intefererence pattern produced by photoelectrons provides holographic snapshots of the photoionization process. Ionization is the dominant response of atoms and molecules to intense laser fields and is at the basis of several important techniques, such as the generation of attosecond pulses that allow the measurement of electron motion in real time. We present experiments in which metastable xenon atoms were ionized with intense 7-micrometer laser pulses from a free-electron laser. Holographic structures were observed that record underlying electron dynamics on a sublaser-cycle time scale, enabling photoelectron spectroscopy with a time resolution of almost two orders of magnitude higher than the duration of the ionizing pulse.

Attosecond Electron Spectroscopy Using a Novel Interferometric Pump-Probe Technique

We present an interferometric pump-probe technique for the characterization of attosecond electron wave packets (WPs) that uses a free WP as a reference to measure a bound WP. We demonstrate our method by exciting helium atoms using an attosecond pulse (AP) with a bandwidth centered near the ionization threshold, thus creating both a bound and a free WP simultaneously. After a variable delay, the bound WP is ionized by a few-cycle infrared laser precisely synchronized to the original AP. By measuring the delay-dependent photoelectron spectrum we obtain an interferogram that contains both quantum beats as well as multipath interference. Analysis of the interferogram allows us to determine the bound WP components with a spectral resolution much better than the inverse of the AP duration.

Beam deviation of large polar molecules in static electric fields: theory and experiment

Abstract A classical approach to calculate the energy and the orientation of symmetric top and linear molecules in high electric fields is proposed. This calculation is particularly well adapted to large molecules. It is used to simulate the deviation of a molecular beam in an inhomogeneous electric field. We give an example of experimental and calculated profiles of deviation for a transition metal-fullerene compound TiC60. This is the first direct measurement of the permanent dipole of a large rigid molecule in the gas phase.

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.

XUV excitation followed by ultrafast non-adiabatic relaxation in PAH molecules as a femto-astrochemistry experiment.

Highly excited molecular species are at play in the chemistry of interstellar media and are involved in the creation of radiation damage in a biological tissue. Recently developed ultrashort extreme ultraviolet light sources offer the high excitation energies and ultrafast time-resolution required for probing the dynamics of highly excited molecular states on femtosecond (fs) (1 fs=10−15s) and even attosecond (as) (1 as=10−18 s) timescales. Here we show that polycyclic aromatic hydrocarbons (PAHs) undergo ultrafast relaxation on a few tens of femtoseconds timescales, involving an interplay between the electronic and vibrational degrees of freedom. Our work reveals a general property of excited radical PAHs that can help to elucidate the assignment of diffuse interstellar absorption bands in astrochemistry, and provides a benchmark for the manner in which coupled electronic and nuclear dynamics determines reaction pathways in large molecules following extreme ultraviolet excitation.

Photoelectron Spectroscopy of Gramicidin Polyanions: Competition between Delayed and Direct Emission

We present the first photoelectron (PE) spectra of polypeptide polyanions. Combining PE spectroscopy and mass spectrometry provides a direct measurement of the stability of the polyanions with respect to electron detachment and of the repulsive energy between excess charges. The second electron affinity of gramicidin was found to amount to 2.35 +/- 0.15 eV, and the value of the repulsive Coulomb barrier was estimated to be 0.5 +/- 0.15 eV. The spectra are interpreted as resulting from a competition between delayed and direct emission.

Characterization of a two-color pump–probe setup at FLASH using a velocity map imaging spectrometer

We report on the implementation of a high-count-rate charged particle imaging detector for two-color pump-probe experiments at the free electron laser in Hamburg (FLASH). In doing so, we have developed a procedure for finding the spatial and temporal overlap between the extreme UV free electron laser (FEL) pulses and the IR pulses, which allows for complete alignment of the setup in situations where the region of overlap between the FEL and the IR is not easily accessible by means of imaging optics.

Single-shot measurement of revival structures in femtosecond laser-induced alignment of molecules.

We present a single-shot detection technique for field-free molecular alignment. The method is based on probing the time-varying birefringence of an aligned sample by use of a chirped probe pulse, thus encoding the dependence of the alignment on time onto the spectral domain. The technique is applied to alignment of O2. The recorded signals are well described by an analytical formula.