Yi. Kharkats et al., COHERENCE, FRICTION, AND ELECTRIC-FIELD EFFECTS IN PRIMARY CHARGE SEPARATION OF BACTERIAL PHOTOSYNTHESIS, Journal of physical chemistry, 99(36), 1995, pp. 13545-13554
New electron transfer patterns have been revealed by the dynamics of t
he special pair chforophyll, the auxiliary chlorophyll, and pheophytin
in primary bacterial photosynthetic charge separation. We address her
e several of these charge transfer features for which new elements of
electron transfer theory, disregarded in common theoretical approaches
to photosynthetic electron transfer, are needed. These features are,
first, an auxiliary chlorophyll state weakly off-resonance relative to
the special pair and pheophytin states. Common superexchange views fa
il in this case, and incorporation of continuous vibrational manifolds
in all three electronic states is essential. Secondly, external elect
ric fields may induce transitions between the superexchange and sequen
tial electron transfer modes where the vibrational manifolds ensure th
at mild resonances rather than divergence appear in the rate constant
at resonance. The sequential mode finally incorporates a variety of fr
ictional patterns ranging from vibrationally almost relaxed transition
s to strongly dynamically coupled, coherent transitions.