Issue 42, 2022

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.

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

Supplementary files

Article information

Article type
30 Jun 2022
04 Oct 2022
First published
24 Oct 2022
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2022,24, 25864-25877

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

A. Šrut, S. Mai, I. V. Sazanovich, J. Heyda, A. Vlček, L. González and S. Záliš, Phys. Chem. Chem. Phys., 2022, 24, 25864 DOI: 10.1039/D2CP02981B

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