Electron spin resonance in zero magnetic field of the reaction center triplet of photosynthetic bacteria.

The decay rates kx, ky, kz of the individual spin levels of the light-induced triplet state have been accurately measured by the zero-field resonance technique under conditions of very low light intensity and a microwave sweep rate of 2.5 MHz/microseconds, which is in excess of that commonly used in optical detection magnetic resonance experiments. The rates ku found correspond well with those previously determined under somewhat different conditions (Hoff, A.J. (1976) Biochim. Biophys. Acta 440, 765--771) and with those inferred from the decay at 4.2 degrees K of the triplet-triplet absorption after picosecond excitation (Parson, W.W. and Monger, T.G. (1977) Brookhaven Symp. Biology 28, 195--212). Thus there seems no reason to doubt that PR corresponds to the triplet state detected by ESR. In a recent publication Clarke and Connors (Clarke, R.H. and Conners, R.E. (1976) Chem. Phys. Lett. 42, 69--72) published values of the rates ku which differ substantially from ours and which lead to a mean lifetime in excess of that of PR. We show that erroneous rates are obtained when the microwave sweep rate is not made fast relative to the decay of the individual spin levels. Zero-field splitting parameters for a member of photosynthetic bacteria have been measured with an accuracy of better than 0.4% for D and 1% for E. The enhanced precision as compared to conventional ESR allows one to discriminate between species of one family. Deuteration reduces the ku values by a factor of about 2, with little spin selectivity. This effect is much larger than previously observed for chlorophyll a. The present results explain the decrease in fluorescence intensity observed on microwave saturation in zero-field optical detection magnetic resonance experiments, and they also show that the simple exciton model is inadequate to derive the geometry of the reaction center dimer from the observed zerofield splitting and decay rates.