Brownian dynamics simulations of intramolecular energy transfer

A novel technique for modelling intramolecular energy transfer is presented. Brownian dynamics calculations are used to compute the trajectories of donor and acceptor species, and the instantaneous orientation factor is calculated during each temporal iteration. In this work, several model systems are considered. Trajectories were computed for energy transfer between a flexible donor and a rigidly fixed acceptor. We have considered configurations where the donor is, (1) tethered to a fixed point in space, but free to diffuse rotationally, and (2) constrained to wobble in a cone. The luminescence decay of the donor is ‘measured’, and a non-single-exponential decay is observed for configurations of efficient energy transfer. Luminescence anisotropy measurements of constrained and unconstrained donors reflect the contribution of both energy transfer and rotational diffusion to the shape of the anisotropy decay curve.