Anomalous pulse-angle and phase dependence of Hahn’s electron spin echo and multiple-quantum echoes of the spin correlated radical pair P700⁺A ⁻₁ in photosystem I

Abstract

In a spin-correlated radical pair system, anomalous pulse-angle and phase dependence of electron spin echo and multiple-quantum echoes were theoretically calculated by Tanget al. (J. Chem. Phys.106, 7471 (1997)). The maximum intensity of the out of phase signal at 45 degree of spin rotation angle was experimentally verified in two-pulse echoes of the light-induced P700⁺A ⁻₁ radical pair in Photosystem I. The values,D = 1.64 G andJ = 0.00 G, fit well with the experimental ESEEM spectra. Single and double quantum echoes were observed at the value oft = τ andT = 2τ with the laser flash-t-P1_70,ζ1-τ-P2_{140, ζ2}-T pulse sequence, which led to determination of the relaxation time T₂₃ between the singlet and triplet ¦T₀〉 states. The relaxation times of the zero and single quantum transitions were determinedT ₂₃ ≈ 100 ns andT ₂ = 1000 ns, respectively. The field sweep ESE signal shape can be fitted with the hyperfine inhomogeneities of 7 G for P700⁺ and of 10 G for A ⁻₁ .