In
Photosystem I (PS I) long-wavelength chlorophylls (LWC) of the core
antenna are known to extend the spectral region up to 750 nm for absorbance
of light that drives photochemistry. Here we present clear evidence
that even far-red light with wavelengths beyond 800 nm, clearly outside
the LWC absorption bands, can still induce photochemical charge separation
in PS I throughout the full temperature range from 295 to 5 K. At
room temperature, the photoaccumulation of P700+• was followed by the absorbance increase at 826 nm. At low temperatures
(T < 100 K), the formation of P700+•FA/B–• was monitored by the characteristic
EPR signals of P700+• and FA/B–• and by the characteristic light-minus-dark absorbance difference
spectrum in the QY region.P700 oxidation was observed
upon selective excitation at 754, 785, and 808 nm, using monomeric
and trimeric PS I core complexes of Thermosynechococcus
elongatus and Arthrospira platensis, which differ in the amount of LWC. The results show that the LWC
cannot be responsible for the long-wavelength excitation-induced charge
separation at low temperatures, where thermal uphill energy transfer
is frozen out. Direct energy conversion of the excitation energy from
the LWC to the primary radical pair, e.g., via a superexchange mechanism,
is excluded, because no dependence on the content of LWC was observed.
Therefore, it is concluded that electron transfer through PS I is
induced by direct excitation of a proposed charge transfer (CT) state
in the reaction center. A direct signature of this CT state is seen
in absorbance spectra of concentrated PS I samples, which reveal a
weak and featureless absorbance band extending beyond 800 nm, in addition
to the well-known bands of LWC (C708, C719 and C740) in the range
between 700 and 750 nm. The present findings suggest that nature can
exploit CT states for extending the long wavelength limit in PSI even
beyond that of LWC. Similar mechanisms may work in other photosynthetic
systems and in chemical systems capable of photoinduced electron transfer
processes in general.