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Energy transfer of the light harvesting complex LHC-II trimer, extracted from spinach, was studied in the Q(y) region at room temperature by femtosecond transient absorption spectroscopy. Configuration interaction exciton method [Linnanto et al. (1999) J Phys Chem B 103: 8739-8750] and 2.72 A structural information reported by Liu et al. was used to calculate spectroscopic properties and excitation energy transfer rates of the complex. Site energies of the pigments and coupling constants of pigment pairs in close contact were calculated by using a quantum chemical configuration interaction method. Gaussian random variation of the diagonal and off-diagonal exciton matrix elements was used to account for inhomogeneous broadening. Rate calculations included only the excitonic states initially excited and probed in the experiments. A kinetic model was used to simulate time and wavelength dependent absorption changes after excitation on the blue side of the Q(y) transition and compared to experimentally recorded rates. Analysis of excitonic wavefunctions allowed identification of pigments initially excited and probed into later. It was shown that excitation of the blue side of the Q(y) band of a single LHC-II complex results in energy transfer from chlorophyll b's of the lumenal side to chlorophyll a's located primarly on one of the monomers of the stromal side.

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Illumination of Ru(dcbpy)I2(CO)2 (dcbpy = 4,4‘-dicarboxy-2,2‘-bipyridine) with (near) ultraviolet light induces dissociation of one of the CO groups of the complex. In solution the opened coordination site of the metal is occupied by a solvent molecule. In the present study the kinetics of the ligand exchange reaction has been studied in solution with femtosecond time resolution by probing the CO stretching vibrations of the reactant and the product molecules Ru(dcbpy)I2(CO)(EtOH) in the infrared and probing electronic transitions in the visible spectral regions. The kinetic results indicate that photoelimination of the CO group occurs on a subpicosecond time scale. The overall quantum yield of the reaction is well below unity (0.3), indicating that the majority of the excited parent molecules does not convert to the product molecules. According to the present observations, recovery of the parent molecule takes place on a subpicosecond time scale. Later time evolution shows relaxation of this state with time constants of 4 and 68 ps. Dissipation of the excess energy of the solvated product is characterized by a biexponential relaxation process with time constants of 18 and 270 ps.