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WIREs Comput Mol Sci
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The sensing mechanism studies of the fluorescent probes with electronically excited state calculations

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Recent research has indicated that fluorescent probes have tremendous potential for the selective detection of chemical and biological species. Over the past decade, researchers have proposed a series of fluorescence‐based sensing mechanisms of such probes by the calculation of their electronic excited states. Investigations of sensing mechanisms have been based on deep insights into the interactions between probe molecules and their target species, as well as their fluorescence properties. Advances in calculation methods, modeling software, and computational power have enabled researchers to use excited‐state theoretical calculations to reproduce experimental fluorescence phenomena and then provide molecular‐level explanations thereof. In this advanced review, we describe the evolution of theoretical studies on excited‐state sensing mechanisms for fluorescent probes that respond to target species. Focusing on calculation methods that facilitate investigation of the photophysical properties and excited‐state dynamics of probes, we emphasize sensing mechanisms mainly reported by our group. Most of these studies have been supported by theoretical predictions based on time‐dependent density functional theory. For this most popular excited‐state calculation method, vertical excitation energy, excited‐state geometrical optimization and a scan of the excited‐state potential energy surface should be noted in the calculation of electronic and molecular differences between the excited‐state probe and its reaction product with the target analyte. These state‐of‐the‐art calculations are of great importance for unraveling details of fluorescence‐based sensing mechanisms, including photochemical reactions (such as twist intramolecular charge transfer and excited‐state proton transfer) and excited‐state electronic processes (such as intramolecular charge transfer and photoinduced electron transfer). These studies have generated new and inspirational mechanistic proposals and have provided a systematic approach for the development of efficient fluorescent sensors. WIREs Comput Mol Sci 2018, 8:e1351. doi: 10.1002/wcms.1351 This article is categorized under: Structure and Mechanism > Computational Biochemistry and Biophysics Theoretical and Physical Chemistry > Spectroscopy
Typical molecular structure of fluorescent probes based on a binding site and a fluorophore. (Reproduced with permission from Ref 23)
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Frontier molecular orbital (FMO) energy illustrations of the donor‐PET (d‐PET) process of the cyanine‐based fluorescent probe 13 and its oxidation product 14. (Reproduced with permission from Ref )
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Frontier molecular orbital (FMO) energy illustrations of acceptor‐PET (a‐PET) process of the cyanine‐based fluorescent probe 11 and its oxidation product 12. (Reproduced with permission from Ref 42)
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Structures of the probe 9 and its oxidation product 10 optimized using density functional theory (DFT) and TDDFT (time‐dependent DFT) at the B3LYP/TZVP/COSMO level. (Reproduced with permission from Ref 41)
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Intramolecular charge transfer (ICT) process provided by frontier molecular orbitals (FMOs) involved in the S1 state of the fluoride probe 7 and its desilylated product 8. (Reproduced with permission from Ref 110)
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S1‐state potential‐energy surface (PES) for the excited‐state proton transfer (ESPT) process in probe 5, calculated at the TDDFT/B3P86/TZVP level. (Reproduced with permission from Ref 83)
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Potential‐energy surface (PES) of the excited‐state proton transfer (ESPT) process for the desilylation product 4 of the probe computed by the TDDFT/B3LYP/TZVP method. (Reproduced with permission from Ref 98)
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Frontier molecular orbitals (FMOs) involved in the S0–S1 transition of the coumarin‐based probe 1 computed at the TDDFT/B3LYP/TZVP level of theory. (Reproduced with permission from Ref )
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Theoretical and Physical Chemistry > Spectroscopy
Structure and Mechanism > Computational Biochemistry and Biophysics

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