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fwhm. The time- resolved spectra show bleaching of the CN fundamental mode of CytcCN and two absorption features at lower energies. The bleach signal and both absorption features are all formed within the time resolution of the experiment (< 200 fs) and decay with a life time of 1.9 ps. One transient absorption feature, appearing immediately red to the bleach signal, results from the thermal excitation of lo w-frequency modes of the heme that an harmonically couple to the CN funda-mental mode, thereby shifting the CN mode to lower energi es. The shift of the CN mode decays with a lifetime of 2 ps, equivalent to the time scale for vibrational cooling of the low-frequency heme modes. The other transient absorp-tion feature, which is 3.3 times weaker than the bleach signal and shifted 27 cm

Picosecond Dynamics of CN--Ligated Ferric Cytochrome c after Photoexcitation Using Time-resolved Vibrational Spectroscopy

Picosecond Dynamics of CN^--Ligated Ferric Cytochrome c after Photoexcitation Using Time-resolved Vibrational Spectroscopy