The Molecular Second Hyperpolarizability of the Light-Harvesting Chlorophyll a/b Pigment-Protein Complex of Photosystem II

Photosynthetic structures when imaged with nonlinear optical microscopy give rise to high third harmonic generation (THG) signal intensity due to the presence of chlorophylls and xanthophylls which have large second hyperpolarizabilitiy (gamma) values. The gamma value of trimers of the light-harvesting chlorophyll a/b pigment-protein complex of photosystem II (LHCII) isolated from pea (Pisum sativum) plants was investigated by the THG ratio technique at 1028 nm wavelength and found to have the value (-1600 +/- 400) X 10(-41) m(2) V-2. The large negative gamma value of trimeric LHCII is due to the presence of chlorophyll a and chlorophyll b which have large negative gamma values, while positive gamma values of xanthophylls reduce the magnitude of the THG signal. Variation was observed between the measured gamma value of LHCII and the approximated gamma value of LHCII obtained by adding individual gamma values of chlorophylls and xanthophylls. This difference can be attributed to the differing inter-pigment interactions of oriented chlorophylls and xanthophylls in the pigment-protein complex compared to randomly oriented non-interacting pigments in solution, as well as a differing dielectric environment of the pigments within LHCII versus the surrounding organic solvent.