Time-resolved high-harmonic spectroscopy of ultrafast photo-isomerization dynamics

Abstract: We report the first study of time-resolved high-harmonic spectroscopy (TR-HHS) of a bond-making chemical reaction. We investigate the transient change of the high harmonic signal from 1,3-cyclohexadiene (CHD), which undergoes ring-opening and isomerizes to 1,3,5-hexatriene (HT) upon photoexcitation. By associating the change of the harmonic yield with the changes of the ionization energy and vibrational frequency of the molecule due to the isomerization, we find that the electronic excited state of CHD created via two-photon absorption of 3.1 eV photons relaxes almost completely within 80 fs to the electronic ground state of CHD with vibrational excitation. Subsequently, the molecule isomerizes abruptly to HT, i.e., ring-opening occurs, around 400 fs after the excitation. The present results demonstrate that TR-HHS, which can track both the electronic and the nuclear dynamics, is a powerful tool for unveiling ultrafast photo-chemical reactions.