The mid- to near-IR difference spectra of optically pumped and
unpumped reaction centers were recorded
over a time range circa 0.1−20 ps allowing us to isolate
kinetically the transient electronic spectra of the
excited special pair P* and its charge-separated form
P+H-. The spectrum of P* between 1 and
5.2 μm
exhibits two main bands, one at 5300 cm-1 and
another at 2710 cm-1, while
P+H- exhibits two bands, one
at 2600 cm-1 and another at 8000
cm-1. These new states do not appear as
transitions of unexcited reaction
centers at E(P*) + 5300 cm-1 or
E(P*) + 2710 cm-1 (although the
former is close to the QX transition region
of the special pair), suggesting that they derive almost exclusively
from charge transfer
(PL
+PM
- or
PL
-PM
+)
states. This conclusion is strengthened by the anisotropies
obtained by pumping P* and probing these transitions
with polarized light. The transition of
P+H- at 2600 cm-1
corresponds to the known hole transfer transition,
and this assignment is confirmed by kinetic and anisotropy
measurements: the transition dipole is along the
direction of charge transfer between PL and PM.
The anisotropy for the transition at 8000
cm-1 is consistent
with a transition dipole along the y-axis of PM,
in agreement with theoretical predictions for a
trip−doublet
transition.