Physical Chemistry

X-Ray Transient Absorption Reveals the 1Au (Nπ*) State of Pyrazine in Electronic Relaxation

Valeriu Scutelnic Department of Chemistry, University of California, Berkeley, CA 94720, USA


Electronic relaxation in organic chromophores often proceeds via states not directly accessible by photoexcitation. We report on the photoinduced dynamics of pyrazine that involves such states, excited by a 267 nm laser and probed with X-ray transient absorption spectroscopy in a table-top setup. In addition to the previously characterized 1B2u (ππ*) (S2) and 1B3u (nπ*) (S1) states, the participation of the optically dark 1Au (nπ*) state is assigned by a combination of experimental X-ray core-to-valence spectroscopy, electronic structure calculations, nonadiabatic dynamics simulations, and X-ray spectral computation. Despite 1Au (nπ*) and 1B3u (nπ*) states having similar energies at relaxed geometry, their X-ray absorption spectra differ largely in transition energy and oscillator strength. The 1Au (nπ*) state is populated about 200 femtoseconds after electronic excitation and plays a key role in the relaxation of pyrazine to the ground state.


Thumbnail image of manuscript_X-ray_transient_absorption_reveals.pdf
download asset manuscript_X-ray_transient_absorption_reveals.pdf 1 MB [opens in a new tab]

Supplementary material

Thumbnail image of Supplementary_material_X-ray_transient_absorption_reveals.pdf
download asset Supplementary_material_X-ray_transient_absorption_reveals.pdf 6 MB [opens in a new tab]
Supplementary material X-ray transient absorption reveals