Fluorescence detected magnetic resonance (FDMR) spectra and fluorescence emission spectra at 4.2 K of chlorophyll-proteins isolated and purified from barley thylakoids are presented. The FDMR spectra show the occurrence of chlorophyll a triplet states in all five chlorophyll-proteins studied, namely Chlu-P1, Chla-P2, Chla-P3, Chla/b-Pl and Chla/b-P2.The presence of more than one chlorophyll triplet each associated with a chlorophyll emitting at a specific wavelength gives rise to a characteristic wavelength dependence of the FDM R spectrum of chlorophyll-proteins. The zero field splitting parameters measured, combined with the observed fluorescence emission wavelengths suggest that three types of interactions of the Mg atom of chlorophyll a occur in these proteins: a type similar to that in the parallel dimer (Chl a. H20)2, seen at 721 nm for Chla-PI leading to a positive FDMR signal; a type like that in Chl a-2 pyridine also giving a positive FDMR signal, seen in Chla-P2 and Chla-P3, and a third type similar to that in Chl a. 2H20 leading to a negative FDMR signal, seen for Chla-PI at 679 nm, and for Chla/b-PI and Chla/b-P2.The FDMR spectrum in the antenna of photosystem I (Chla-P1)can probably be ascribed to that of a trap formed by a pair of interacting chlorophyll a molecules, indicating that the organisation of chlorophyll in the antenna may not in principle be very different from that in the photosystem I reaction centre, and that it contains approximately plane-parallel chlorophyll a pairs. Chla-P2 and Chla-P3 do not show a long wavelength (> 700 nm) emission, suggesting a much weaker interaction between chlorophyll molecules in these proteins compared to that in Chla-P1. For Chla/o-Pl and Chla/0-P2 the absence of a long wavelength emission and the observation of zero field splitting (ZFS) parameters similar to that of monomeric Chl a. 2H20 both indicate the absence of strong interactions between chlorophyll a molecules in these proteins also, and it is suggested that chlorophyll a and chlorophyll b molecules occur in interacting pairs. (8,9,26). Since a magnetic field is absent, there is no need to use oriented samples, such as single crystals, in order to obtain magnetic resonance spectra with satisfactory resolution (-10-2). In addition, optical detection of magnetic resonance transitions is well-known to be very sensitive as compared with detection of microwave-absorption by diodes or bolometers, such as in conventional high-field electron paramagnetic resonance (EPR) spectroscopy (1 I). This combination of properties makes FDMR spectroscopy an ideal technique for studying complex systems, such as the chlorophyll-proteins of a photosynthetic membrane which can be obtained only in limited amounts and in non-oriented form.Triplet state FDMR spectroscopy makes use of the fact, that the three-fold degeneracy of the molecular triplet state is lifted by spin-spin interaction, even in the absence of an external magnetic field. For photosynthetic pigments, the resulting zero field splittings (ZFS) are 10-2cm...