WAVE PACKET MOTIONS COUPLED TO ELECTRON TRANSFER IN REACTION CENTERS OF CHLOROFLEXUS AURANTIACUS

Abstract

Transient absorption difference spectroscopy with ~20 femtosecond (fs) resolution was applied to study the time and spectral evolution of low-temperature (90 K) absorbance changes in isolated reaction centers (RCs) of Chloroflexus (C.) aurantiacus. In RCs, the composition of the B-branch chromophores is different with respect to that of purple bacterial RCs by occupying the BB binding site of accessory bacteriochlorophyll by bacteriopheophytin molecule (ΦB). It was found that the nuclear wave packet motion induced on the potential energy surface of the excited state of the primary electron donor P* by ~20 fs excitation leads to a coherent formation of the states [Formula: see text] and [Formula: see text] (BA is a bacteriochlorophyll monomer in the A-branch of cofactors). The processes were studied by measuring coherent oscillations in kinetics of the absorbance changes at 900 nm and 940 nm (P* stimulated emission), at 750 nm and 785 nm (ΦB absorption bands), and at 1,020–1028 nm ([Formula: see text] absorption band). In RCs, the immediate bleaching of the P band at 880 nm and the appearance of the stimulated wave packet emission at 900 nm were accompanied (with a small delay of 10–20 fs) by electron transfer from P* to the B-branch with bleaching of the ΦB absorption band at 785 nm due to [Formula: see text] formation. These data are consistent with recent measurements for the mutant HM182L Rb. sphaeroides RCs (Yakovlev et al., Biochim Biophys Acta1757:369–379, 2006). Only at a delay of 120 fs was the electron transfer from P* to the A-branch observed with a development of the [Formula: see text] absorption band at 1028 nm. This development was in phase with the appearance of the P* stimulated emission at 940 nm. The data on the A-branch electron transfer in C. aurantiacus RCs are consistent with those observed in native RCs of Rb. sphaeroides. The mechanism of charge separation in RCs with the modified B-branch pigment composition is discussed in terms of coupling between the nuclear wave packet motion and electron transfer from P* to ΦB and BA primary acceptors in the B-branch and A-branch, respectively.