Ultrafast electronic and vibrational dynamics of a ruthenium porphyrin complex in intersystem crossing

Abstract

Using sub-5fs visible laser pulses, ultrafast time-resolved absorption change was observed for Ru(II)(TPP)(CO) (TPP=5,10,15,20-tetraphenylporphirine) solved in chloroform. Exponential fitting of the time traces estimated decay life times of intermediates as 230 +/- 70 fs, 1150 +/- 260 fs, 2150 +/- 360 fs, and "4.8 ps for (1)Q(x(1,0))(pi,pi*), (1)Q(x(0,0))(pi,pi*), (3)(d, pi*), and (3)(pi, pi*), respectively. Real-time change of instantaneous molecular vibration frequency was studied by spectrogram analysis, which reflects gradual vibration mode change in the intersystem crossing from singlet state to triplet state. (C) 2011 Published by Elsevier B. V.