TY - JOUR A1 - Preiss, J. A1 - Kage, Daniel A1 - Hoffmann, Katrin A1 - Martínez, T. J. A1 - Resch-Genger, Ute A1 - Presselt, M. T1 - Ab initio prediction of fluorescence lifetimes involving solvent environments by means of COSMO and vibrational broadening JF - The Journal of Physical Chemistry A N2 - The fluorescence lifetime is a key property of fluorophores that can be utilized for microenvironment probing, analyte sensing, and multiplexing as well as barcoding applications. For the rational design of lifetime probes and barcodes, theoretical methods have been developed to enable the ab initio prediction of this parameter, which depends strongly on interactions with solvent molecules and other chemical species in the emitters' immediate environment. In this work, we investigate how a conductor-like screening model (COSMO) can account for variations in fluorescence lifetimes that are caused by such fluorophore−solvent interactions. Therefore, we calculate vibrationally broadened fluorescence spectra using the nuclear ensemble method to obtain distorted molecular geometries to sample the electronic transitions with time-dependent density functional theory (TDDFT). The influence of the solvent on fluorescence lifetimes is accounted for with COSMO. For example, for 4-hydroxythiazole fluorophore containing different heteroatoms and acidic and basic moieties in aprotic and protic solvents of varying polarity, this approach was compared to experimentally determined lifetimes in the same solvents. Our results demonstrate a good correlation between theoretically predicted and experimentally measured fluorescence lifetimes except for the polar solvents Ethanol and acetonitrile that can specifically interact with the heteroatoms and the carboxylic acid of the thiazole derivative. KW - Fluorescence lifetime KW - Ab initio calculation KW - COSMO KW - Conductor-like screening model PY - 2018 DO - https://doi.org/10.1021/acs.jpca.8b08886 SN - 1089-5639 SN - 1520-5215 VL - 122 IS - 51 SP - 9813 EP - 9820 PB - American Chemical Society CY - Washington, DC AN - OPUS4-47177 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -