In this illustration, ultrashort X-ray pulses (pink) at the Linac Coherent Light Source ionize neon gas at the center of a ring of detectors. An infrared laser (orange) sweeps the outgoing electrons (blue) across the detectors with circularly polarized light. (Terry Anderson / SLAC National Accelerator Laboratory)

To catch chemistry in action, scientists at the Department of Energy’s SLAC National Accelerator Laboratory use the shortest possible flashes of X-ray light to create “molecular movies” that capture the motions of atoms in chemical reactions and reveal new details about the most fundamental processes in nature.

Future experiments at the Linac Coherent Light Source (LCLS), SLAC’s X-ray free-electron laser, will use pulses that last just attoseconds (billionths of a billionth of a second). Such experiments will be even more powerful because they'll be able to detect the motions of electrons within molecules during chemical reactions. However, to design such ultrafast experiments, researchers need meticulous measurements of the X-ray pulses so they can use that information to interpret the data they collect on the samples they study.

Now an international team, including SLAC scientists, has created an X-ray “attoclock” that lets them analyze X-ray pulses on the attosecond timescale of electron motions. “Using this method, we can resolve details of the pulses in the attosecond domain for the first time,” says Ryan Coffee, a senior scientist at LCLS and the Stanford PULSE Institute and a principal investigator on the team. “This paves the way for X-ray free-electron laser science at a timescale that is key to understanding physical chemistry.”

The term “attoclock” was coined by Swiss physicist Ursula Keller, who first demonstrated a technique to study attosecond processes with circularly polarized light 10 years ago. However, the LCLS version is the first one designed to measure individual X-ray pulses, one by one. It consists of a ring of detectors arranged like numbers on the face of a clock. When an X-ray pulse hits a target at the center of the clock, it knocks electrons out of the target's atoms. Those electrons are hit by circularly polarized laser light that whirls the electrons around the ring before they land on one of the detectors. The position of that detector – the number on the clock face – tells scientists how much energy the X-ray pulse contained and when exactly it hit the target.

“It’s like reading a watch,” Coffee says. “An electron may strike a detector positioned at one o’clock or three o’clock or anywhere around the clock face. We can tell from where it hits exactly when it was generated by the X-ray pulse.”

In an experiment designed to test the technique, the researchers hit neon gas with an attosecond X-ray pulse and then read which of the 16 detectors arrayed around the attoclock the freed electrons hit. The technique will be especially important for pump-probe experiments, in which a molecule is first excited with a “pump” pulse and then analyzed by a second “probe” pulse to see how it reacted.

As short as they are, these pulses can contain many different colors or wavelengths. “The color can also vary widely from pulse to pulse, and our technique can sift through the pulses, finding those that are interesting for the experiment,” Coffee says, noting the importance that such sifting will have for the data deluge expected when an upgrade to the X-ray laser, LCLS-II, comes online a couple years from now. With pulses that arrive up to a million times per second, LCLS-II will produce as much data in a few minutes as LCLS currently collects in a month. What’s more, scientists can potentially excite individual elements in separate parts of the molecule at the same time using different colors of X-rays.