Short- and Long-Range Solvation Effects on the Transient UV-Vis Absorption Spectra of a Ru(II)-Polypyridine Complex Disentangled by Nonequilibrium Molecular Dynamics
Authors: Prampolini G., Ingrosso F., Cerezo J., Iagatti A., Foggi P., Pastore M.
Autors Affiliation: CNR, Ist Chim Composti OrganoMetall ICCOM, Area Ric, Via G Moruzzi 1, I-56124 Pisa, Italy; Univ Lorraine, F-54000 Nancy, France; CNRS, LPCT, F-54000 Nancy, France; Univ Autonoma Madrid, Fac Ciencias, Dept Quim, E-28049 Madrid, Spain; Univ Firenze, European Lab Non Linear Spect LENS, Via Nello Carrara 1, I-50019 Florence, Italy; CNR, INO, Largo Fermi 6, I-50125 Florence, Italy; Univ Perugia, Dipartimento Chim Biol & Biotecnol, Via Elce Sotto 8, I-06123 Perugia, Italy
Abstract: Evidence of subtle effects in the dynamic reorganization of a protic solvent in its first- and farther-neighbor shells, in response to the sudden change in the solute’s electronic distribution upon excitation, is unveiled by a multilevel computational approach. Through the combination of nonequilibrium molecular dynamics and quantum mechanical calculations, the experimental time evolution of the transient T-1 absorption spectra of a heteroleptic Ru(II)-polypyridine complex in ethanol or dimethyl sulfoxide solution is reproduced and rationalized in terms of both fast and slow solvent reequilibration processes, which are found responsible for the red shift and broadening experimentally observed only in the protic medium. Solvent orientational correlation functions and a time-dependent analysis of the solvation structure confirm that the initial, fast observed red shift can be traced back to the destruction-formation of hydrogen bond networks in the first-neighbor shell, whereas the subsequent shift, evident in the [20-500] ps range and accompanied by a large broadening of the signal, is connected to a collective reorientation of the second and farther solvation shells, which significantly changes the electrostatic embedding felt by the excited solute.
Journal/Review: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume: 10 (11) Pages from: 2885 to: 2891
KeyWords: TRIPLET EXCITED-STATE; ELECTRON LOCALIZATION DYNAMICS; CHARGE-TRANSFER PROCESS; ENERGY-TRANSFER; SOLVENT; SPECTROSCOPY; SOLAR; PHOTOCHEMISTRY; PHOTOPHYSICS; SEPARATIONDOI: 10.1021/acs.jpclett.9b00944Citations: 6data from “WEB OF SCIENCE” (of Thomson Reuters) are update at: 2021-10-17References taken from IsiWeb of Knowledge: (subscribers only)Connecting to view paper tab on IsiWeb: Click hereConnecting to view citations from IsiWeb: Click here