We revise the interpretation of coherence signals in photosynthetic systems and clarify what they tell us about light harvesting.

The time-resolved orientational anisotropies of the OD hydroxyl stretch of dilute HOD in H2O confined on a nanometer length scale in sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles are studied using ultrafast infrared polarization and spectrally resolved pump-probe spectroscopy, and the results are compared to the same experiments on bulk water. The orientational anisotropy data for three water nanopool sizes (4.0, 2.4, and 1.7nm) can be fitted well with biexponential decays. The biexponential decays are analyzed using a wobbling-in-a-cone model that involves fast orientational diffusion within a cone followed by slower, full orientational relaxation. The data provide the cone angles, the diffusion constants for motion within the cones, and the final diffusion constants as a function of the nanopool size. The two processes can be interpreted as a local angular fluctuation of the OD and a global hydrogen bond network rearrangement process. The trend in the relative amplitudes of the long and short exponential decays suggest an increasing rigidity as the nanopool size decreases. The trend in the long decay constants indicates a longer hydrogen bond network rearrangement time with decreasing reverse micelle size. The anisotropy measurements for the reverse micelles studied extrapolate to ∼0.33 rather than the ideal value of 0.4, suggesting the presence of an initial inertial component in the anisotropy decay that is too fast to resolve. The very fast decay component is consistent with initial inertial orientational motion that is seen in published molecular-dynamics simulations of water in AOT reverse micelles. The angle over which the inertial orientational motion occurs is determined. The results are in semiquantitative agreement with the molecular-dynamics simulations.

We present the theory and the selection procedure of phase-cycling schemes for phase coherent multidimension optical spectroscopy. We apply our selection procedure to determine the phase-cycling schemes with the least number of steps needed to measure the two-dimensional spectra of various time resolved four wave mixing optical processes. The phase-cycling scheme selection procedure presented in this paper can be applied to higher order nonlinear optical experiments involving more optical pulses that measure higher dimensional optical spectra.

The dynamics of water, confined on a nanometer length scale (1.7 to 4.0 nm) in sodium bis-(2-ethylhexyl) sulfosuccinate reverse micelles, is directly investigated using frequency resolved infrared vibrational echo experiments. The data are compared to bulk water and salt solution data. The experimentally determined frequency-frequency correlation functions show that the confined water dynamics is substantially slower than bulk water dynamics and is size dependent. The fastest dynamics ($\sim 50\mathrm{f}\mathrm{s}$) is more similar to bulk water, while the slowest time scale dynamics is much slower than water, and, in analogy to bulk water, reflects the making and breaking of hydrogen bonds.