An investigation of the excitation and emission properties of fluorescence compounds using DFT and TD-DFT methods

Duong Tuan Quang



The density functional theory and time-dependent density functional theory methods were used for investigation of the excitation and emission properties of some fluorophores. The calculations were based on the optimized geometries of ground states and excited states at the B3LYP functional and LanL2DZ basis set. The results clarified the nature of the optical properties of the compounds and agreed well with the experimental data. The approximate values of excitation energies and emission energies of compounds were also identified. The calculated excitation energies were about 0.01 to 0.56 eV higher than experimental values. Meanwhile, the emission energies were from 0.34 to 0.89 eV higher than experimental values. These large errors occurred when there were great variations between the optimized geometries of ground state and excited states. They could be due to the presence of components of solvent in real solution that stabilized the excited states, leading to reduce the excitation and emission energies in the experiments.


TD-DFT, fluorescence, absorption, emission, coumarin


Juan CS, Alfonso BC (2017). Fluorescence Microscopy in Life Sciences. Bentham Science Publishers, ISBN 978-1-68108-519-7.

Bernard V (2001). Molecular Fluorescence: Principles and Applications. Wiley-VCH Verlag GmbH, Weinheim – New York – Chichester – Brisbane – Singapore – Toronto, ISBN 3-527-29919-X.

Hien NK, Nhan DT, Kim WY, Bay MV, Nam PC, Van DU, Lim IT, Kim JS, Quang DT (2018). Exceptional case of Kasha's rule: Emission from higher-lying singlet electron excited states into ground states in coumarin-based biothiol sensing. Dyes and Pigments, 152, 118-126.

Nhan DT, Hien NK, Duc HV, Nhung TNA, Trung NT, Van DU, Shin WS, Kim JS, and Quang DT (2016). A hemicyanine complex for the detection of thiol biomolecules by fluorescence. Dyes and Pigments, 131, 301-306.

Godbey WT (2014). An Introduction to Biotechnology: The Science, Technology and Medical Applications. Academic Press, ISBN: 978-1-907568-28-2.

Shahzad A, Köhler G, Knapp M, Gaubitzer E, Puchinger M, and Edetsberger M (2009). Emerging applications of fluorescence spectroscopy in medical microbiology field. Journal of Translational Medicine, 7: 99.

Dai HQ, Tri NN, Trang NTT, Trung NT (2014). Remarkable effects of substitution on stability of complexes and origin of the C–H⋯O(N) hydrogen bonds formed between acetone's derivative and CO2, XCN (X = F, Cl, Br). Royal Society of Chemistry Advances, 4, 13901–13908.

Karabacak M, Cinar M, Kurt M, Poiyamozhi A, Sundaraganesan N (2014). The spectroscopic (FT-IR, FT-Raman, UV and NMR) first order hyperpolarizability and HOMO–LUMO analysis of dansyl chloride. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 117, 234–244.

Keawwangchai T, Morakot N, Wanno B (2013). Fluorescent sensors based on BODIPY derivatives for aluminium ion recognition: an experimental and theoretical study. Journal of Molecular Modeling, 19(3), 1435–1444.

Keawwangchai T, Wanno B, Morakot N, Keawwangchai S (2013). Optical chemosensors for Cu(II) ion based on BODIPY derivatives: an experimental and theoretical study. Journal of Molecular Modeling, 19(10), 4239–4249.

Frisch MJ et al (2009). Gaussian 09, Revision E.01. Wallingford CT: Gaussian Inc.

Hien NK, Bao NC, Nhung NTA, Trung NT, Nam PC, Duong T, Kim JS, Quang DT (2015). A highly sensitive fluorescent chemosensor for simultaneous determination of Ag(I), Hg(II), and Cu(II) ions: Design, synthesis, characterization and application. Dyes and Pigments, 116, 89-96.

Nhan DT, Nhung NTA, Vien V, Trung NT, Cuong ND, Bao NC, Huong DQ, Hien NK, Quang DT (2017). A Benzothiazolium-derived colorimetric and fluorescent chemosensor for detection of Hg2+ ions. Chemistry Letters, 46(1), 135-138.

Stratmann RE, Scuseria GE, Frisch MJ (1998). An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules. Journal of Chemical Physics, 109(19), 8218-8224.

Carlo A, Denis J (2013). The calculations of excited-state properties with time-dependent density functional theory. Chemical Society Reviews, 42, 845-856.

Becke AD (1993). Density-functional thermochemistry. III. The role of exact exchange. The Journal of Chemical Physics, 98, 5648-5652.

Lee C, Yang W, Parr PG (1998). Development of the colle-salvetti correlation-energy formula into a functional of the electron density. Phys Rev B Condens Matter, 37(2), 785-789.

Zamojc K, Wiczk W, Zaborowski B, Jacewicz D, Chmurzynski L (2015). Fluorescence quenching of 7-amino-4-methylcoumarin by different TEMPO derivatives. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 136, 1875–1880.

Sherman WS and Robins E (1998). Fluorescence of substituted 7-hydroxycoumarins. Analytical Chemistry, 40(4), 803-805.

Sharma VK, Mohan D, Sahare PD (2007). Fluorescence quenching of 3-methyl 7-hydroxyl coumarin in presence of acetone. Spectrochimica Acta Part A, 66, 111–113.

Petr K, Jakob W (2009). Photochemistry of organic compounds: from concepts to practice. A John Wiley and Sons Ltd, United Kingdom.