Nonadiabatic excited-state dynamics of ReCl(CO)3(bpy) in two different solvents

We present a study of excited-states relaxation of the complex ReCl(CO)(3)(bpy) (bpy = 2,2-bipyridine) using a nonadiabatic TD-DFT dynamics on spin-mixed potential energy surfaces in explicit acetonitrile (ACN) and dimethylsulfoxide (DMSO) solutions up to 800 fs. ReCl(CO)(3)(bpy) belongs to a group of important photosensitizers which show ultrafast biexponential subpicosecond fluorescence decay kinetics. The choice of solvents was motivated by the different excited-state relaxation dynamics observed in subpicosecond time-resolved IR (TRIR) experiments. Simulations of intersystem crossing (ISC) showed the development of spin-mixed states in both solvents. Transformation of time-dependent populations of spin-mixed states enabled to monitor the temporal evolution of individual singlet and triplet states, fitting of bi-exponential decay kinetics, and simulating the time-resolved fluorescence spectra that show only minor differences between the two solvents. Analysis of structural relaxation and solvent reorganization employing time-resolved proximal distribution functions pointed to the factors influencing the fluorescence decay time constants. Nonadiabatic dynamics simulations of time-evolution of electronic, molecular, and solvent structures emerge as a powerful technique to interpret time-resolved spectroscopic data and ultrafast photochemical reactivity.

Automated summary

We studied the excited-state relaxation of the complex ReCl(CO)(3)(bpy) in acetonitrile and dimethylsulfoxide solutions using nonadiabatic TD-DFT dynamics. By simulating the time-dependent populations of spin-mixed states, we monitored the temporal evolution of singlet and triplet states, fitted the bi-exponential decay kinetics, and simulated the time-resolved fluorescence spectra. Analysis of structural relaxation and solvent reorganization helped identify the factors influencing the fluorescence decay time constants.