Clocking transient chemical changes by ultrafast electron diffraction

With the advent of femtosecond (fs) time resolution in spectroscopic experiments, it is now possible to study the evolution of nuclear motions in chemical and photobiochemical reactions. In general, the reaction is clocked by an initial fs laser pulse (which establishes a zero of time) and the dynamics are probed by a second fs pulse; the detection methods include conventional and photoelectron spectroscopy and mass spectrometry1–4. Replacing the probe laser with electron pulses offers a means for imaging ultrafast structural changes with diffraction techniques5–8, which should permit the study of molecular systems of greater complexity (such as biomolecules). On such timescales, observation of chemical changes using electron scattering is non-trivial, because space-charge effects broaden the electron pulse width and because temporal overlap of the (clocking) photon pulse and the (probe) electron pulse must be established. Here we report the detection of transient chemical change during molecular dissociation using ultrafast electron diffraction. We are able to detect a change in the scattered electron beam with the zero of time established unambiguously and the timing of the changes clocked in situ. This ability to clock changes in scattering is essential to studies of the dynamics of molecular structures.