Imaging conical intersection dynamics during azobenzene photoisomerization by ultrafast X-ray diffraction

X-ray diffraction is routinely used for structure determination of stationary molecular samples. Modern X-ray photon sources, e.g., from free-electron lasers, enable us to add temporal resolution to these scattering events, thereby providing a movie of atomic motions. We simulate and decipher the various contributions to the X-ray diffraction pattern for the femtosecond isomerization of azobenzene, a textbook photochemical process. A wealth of information is encoded besides real-time monitoring of the molecular charge density for the cis to trans isomerization. In particular, vibronic coherences emerge at the conical intersection, contributing to the total diffraction signal by mixed elastic and inelastic photon scattering. They cause distinct phase modulations in momentum space, which directly reflect the real-space phase modulation of the electronic transition density during the nonadiabatic passage. To overcome the masking by the intense elastic scattering contributions from the electronic populations in the total diffraction signal, we discuss how this information can be retrieved, e.g., by employing very hard X-rays to record large scattering momentum transfers.

Automated summary

X-ray diffraction is commonly used for structure determination of stationary molecular samples, but modern X-ray photon sources can provide temporal resolution to these scattering events. Studying the femtosecond isomerization of azobenzene, researchers simulate and decipher various contributions to the X-ray diffraction pattern and discuss methods to retrieve information by employing very hard X-rays.