Lund University > Chemical Center > Chemical Physics > Research > Projects > Time-resolved X-ray measurements

Time-resolved X-ray measurements

People involved: Wilfred Fullagar
Former members: Sophie Canton, Jens Uhlig, Monika Walczak, Niklas Gador, Erhan Cengiz

This project is related to the following Fields, Subjects and Techniques:

Fields: Ultrafast Chemistry, Physics and Biology, Photochemistry and Photophysics
Subjects: Photosynthesis, Dye-sensitized Solar Cells, Nanostructures, Metal Complexes, Reaction Dynamics
Techniques: In-house X-ray sources, X-ray detection, Time resolved synchrotron measurements

Time Resolved Measurements

example for energytransfer
The photochemistry and photo dynamics of molecules in nature and artificial systems is a heavily investigated field of research and of great public interest. Applications range from solar cells and artificial photosynthesis, through photoisomerization and dissociation to organic light emitting diodes (OLEDs). Processes of interest include light induced electron transfer and ligand dynamics in transition metal complexes and multichromophoric systems as well as bond breaking and formation in reactive systems. By probing structural changes we can obtain detailed mechanisms of chemical reactions and answer questions like: Which bonds are broken and formed during a chemical reaction? How are ligands interacting with an active site in an enzyme? How is the electronic structure of a molecule changed during a chemical reaction?

Time resolved structural measurements lead to an intimate understanding of the processes occuring in photoexcited systems, which typically take place in the subpicosecond time regime. To catch a snapshot of molecules undergoing such fundamental processes, correspondingly short pulses of radiation are needed. A short pulse of light is an effective way to trigger many fundamental chemical processes. After a suitable delay the system can be interrogated using a second pulse, which may be a very different form of radiation. Structural measurements require that this second pulse has a wavelength comparable to bond lengths. Elsewhere we motivate the use of polychromatic X-rays (or through them, electrons in EXAFS experiments). Measuring at different delay times allows reconstruction of the evolution of the molecular structure following the first pulse.

There are numerous approaches to the production of subpicosecond bursts of X-ray radiation. The common feature is the acceleration or deceleration of charged particles, in most cases electrons. At sub-relativistic energies, ultrashort laser pulses can be used to generate hot electrons with sufficient energy for bremsstrahlung X-ray production. High Harmonic Generation can also be considered as a form of coherent bremsstrahlung radiation, capable of delivering collimated sub-femtosecond X-ray pulses. When the charged particles are moving at relativistic velocities, there is usually a corresponding collimation of the radiation they produce. Among the possibilities to generate X-ray pulses are bend magnet/wiggler radiation, undulator/free electron laser radiation, Smith-Purcell radiation, transition radiation, parametric X-radiation, channel radiation, Thomson scattering and reverse Compton scattering. To a large extent, the characteristics of the electron beam dictate the properties of the resulting X-rays. The necessary relativistic electron beams are conventionally generated using linear accelerators in large scale facilities. However, entirely laser-based plasma wakefield acceleration approaches have been established in recent years. The latter approaches allow far more compact and affordable apparatus in considerably more widespread facilities. Betatron oscillations of electrons in the latter schemes also leads to ultrashort X-ray pulses.

Several of these X-ray generation approaches are being pursued in Lund and we are very much involved in the associated developments, especially in the context of their potential for ultrafast pump-probe Laue crystallography and EXAFS. Meanwhile, the main focus of our work is a small tabletop X-ray source based on a moderate power femtosecond laser. Detectors play a novel and critical role in the practical use of this source, which we believe we are the first to propose. Laser requirements for this approach are not particularly demanding, such that suitable systems are already in widespread use in most laboratories undertaking ultrafast optical measurements. One foreseeable arrangement for pump-probe EXAFS measurements using this apparatus is shown below.

Basic Pump-probe setup with laser path way and waterjetsource
Experimental setup for time resolved X-ray spectroscopy using subpicosecond laser generated X-ray pulses. The chemical reaction is initiated by a short optical pulse (orange laser path). Some time later, a polychromatic X-ray pulse is generated at the surface of the X-ray generation jet, via the red laser path. The setup can be operated under helium, which obviates the need for vacuum apparatus and permits a great diversity of samples. A low-resolution X-ray absorption spectrum is shown, measured using a direct detection CCD.

Further reading and Techniques applied

General overview and motivation for X-ray based measurements
X-ray absorption spectroscopy
X-ray Diffraction and the argumentation for broad bandwidth

Overview and motivation for ultrafast X-ray measurements (This page)
Developments done on ultrafast X-ray sources in Lund
Developments on X-ray Detectors

Measurements done on ultrafast synchrotron user facilities
Steady state measurements done on synchrotrons

Last update: 17 December 2007
Maintained by: Jens Uhlig