Primary Electronic and Vibrational Dynamics of Cytochrome Observed by Sub-10 fs NUV Laser Pulses.

The primary reaction mechanism of cytochrome (Cyt ) was elucidated for two redox forms of ferric (oxidized) and ferrous (reduced) Cyt by measuring their transient absorption (TA) spectra using a homemade sub-10 fs broadband NUV laser pulses system. The TA traces measured in the broad probe wavelength region were analyzed by the global analysis method to study the electronic dynamics. The difference of relaxation dynamics dependent on the excitation bandwidth enabled us to elucidate that the 2.5 ps component in ferrous Cyt can be assigned to intramolecular vibration energy redistribution and not to vibrational cooling, which was not clear until this work. The temporal resolution of 10 fs observes TA signal modulation caused by the molecular vibration in the time domain, which can be used to calculate the instantaneous frequency of the molecular vibration mode. The observed vibrational dynamics has visualized that the heme structure changes in 0.8 ps for ferric Cyt and in >1.0 ps for ferrous Cyt . These estimated lifetimes of vibrational dynamics reflect vibrational relaxation in the ground state of ferric Cyt and electronic transition from the S2 state to the S1 state in ferrous Cyt , respectively.