Nonadiabatic excited-state dynamics of ReCl(CO) 3 (bpy) in two different solvents.
Adam ŠrutSebastian MaiIgor V SazanovichJan HeydaAntonín VlčekLeticia GonzálezStanislav ZálišPublished in: Physical chemistry chemical physics : PCCP (2022)
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.
Keyphrases
- single molecule
- molecular dynamics
- energy transfer
- density functional theory
- ionic liquid
- room temperature
- quantum dots
- molecular docking
- photodynamic therapy
- computed tomography
- magnetic resonance imaging
- high resolution
- pseudomonas aeruginosa
- big data
- transition metal
- artificial intelligence
- molecular dynamics simulations
- candida albicans
- crystal structure