Ab Initio Prediction of Fluorescence Lifetimes Involving Solvent Environments by Means of COSMO and Vibrational Broadening
| Autor: | Martin Presselt, Todd J. Martínez, Julia Preiss, Ute Resch-Genger, Katrin Hoffmann, Daniel Kage |
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| Rok vydání: | 2018 |
| Předmět: |
Fluorophore
010304 chemical physics Time-dependent density functional theory 010402 general chemistry 01 natural sciences Fluorescence 0104 chemical sciences Chemical species chemistry.chemical_compound Molecular geometry chemistry Chemical physics 0103 physical sciences Molecule Density functional theory Physical and Theoretical Chemistry Acetonitrile |
| Zdroj: | The Journal of Physical Chemistry A. 122:9813-9820 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/acs.jpca.8b08886 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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