Maximizing the efficiency of solar energy conversion using dye assemblies rests on understanding where the energy goes following absorption. Transient spectroscopies in solution are useful for this purpose, and the time-resolved data are usually analyzed with a sum of exponentials. This treatment assumes that dynamic events are well separated in time, and that the resulting exponential prefactors and phenomenological lifetimes are related directly to primary physical values. Such assumptions break down for coincident absorption, emission, and excited state relaxation that occur in transient absorption and photoluminescence of tris(2,2′-bipyridine)ruthenium^{2+} derivatives, confounding the physical meaning of the reported lifetimes. In this work, inductive modeling and stochastic chemical kinetics are utilized to develop a detailed description of the primary ultrafast photophysics in transient spectroscopies of a series of Ru dyes, as an alternative to sums of exponential analysis. Commonly invoked three-level schemes involving absorption, intersystem crossing (ISC), and slow nonradiative relaxation and incoherent emission to the ground state cannot reproduce the experimentally measured spectra. The kinetics simulations reveal that ultrafast decay from the singlet excited state manifold to the ground state competes with ISC to the triplet excited state, whose efficiency was determined to be less than unity. The populations predicted by the simulations are used to estimate the magnitudes of transition dipoles for excited state excitations and evaluate the influence of specific ligands. The mechanistic framework and methodology presented are entirely general, applicable to other dye classes, and can be extended to include charge injection by molecules bound to semiconductor surfaces.

Cheshire, T. P.; Brennaman, M. K.; Giokas, P. G.; Zigler, D. F.; Moran, A. M.; Papanikolas, J. M.; Meyer, G. J.; Meyer, T. J.; Houle, F. A. Ultrafast Relaxations in Ruthenium Polypyridyl Chromophores Determined by Stochastic Kinetics Simulations. J. Phys. Chem. B **2020**, *124* (28), 5971-5985. http://dx.doi.org/10.1021/acs.jpcb.0c03110