A DFT/TDDFT investigation of the excited state proton transfer reaction of fisetin chromophore

Yang, Dapeng; Zhao, Jinfeng; Zheng, Rui; Wang, Yusheng; Lv, Jian

doi:10.1016/j.saa.2015.06.098

Cited by 33 publications

(16 citation statements)

References 71 publications

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“…Geometry optimizations of the Bis‐HPBT‐N, Bis‐HPBT‐SPT, and Bis‐HPBT‐DPT forms were performed via DFT descriptions of the electronic structure for the S 0 state and TDDFT descriptions of the S 1 state. Herein, we want to mention that TDDFT method is suitable for this system, because TDDFT has been previously shown to be a very useful tool to describe hydrogen bonding in the excited states of possibly hydrogen‐bond system . Becke's 3‐parameter hybrid exchange functional with Lee‐Yang‐Parr gradient‐corrected correlation (B3LYP functional) was used in both the DFT and TDDFT calculations .…”

Section: Computational Detailsmentioning

confidence: 99%

A theoretical study on the ESPT mechanism for a novel Bis‐HPBT fluorophore

Zhai

Zhang

Song

2018

J of Physical Organic Chem

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In this work, based on the density functional theory and time-dependent density functional theory methods, the properties of the 2 intramolecular hydrogen bonds (O1-H2···N3 and O4-H5···N6) of a new photochemical sensor 4-(3-thiazol-2-yl)-6tert-butyl phenol (Bis-HPBT) have been investigated in detail. The calculated dominating bond lengths and bond angles about these 2 hydrogen bonds (O1-H2···N3 and O4-H5···N6) demonstrate that the intramolecular hydrogen bonds should be strengthened in the S 1 state. In addition, the variations of hydrogen bonds of Bis-HPBT have been also testified based on infrared vibrational spectra. Our theoretical results reproduced absorption and emission spectra of the experiment, which verifies that the theoretical level we used is reasonable and effective in this work. Further, hydrogen bonding strengthening manifests the tendency of excited state intramolecular proton transfer (ESIPT) process.Frontier molecular orbitals depict the nature of electronically excited state and support the ESIPT reaction. According to the calculated results of potential energy curves along stepwise and synergetic O1-H2 and O4-H5 coordinates, the potential energy barrier of approximately 1.399 kcal/mol is discovered in the S 1 state, which supports the single ESIPT process along with 1 hydrogen bond of Bis-HPBT. In other words, the proton transfer reaction can be facilitated based on the electronic excitation effectively. In turn, through the process of radiative transition, the proton-transfer Bis-HPBT-SPT form regresses to the ground state with the fluorescence of 539 nm.

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Section: Computational Detailsmentioning

confidence: 99%

A theoretical study on the ESPT mechanism for a novel Bis‐HPBT fluorophore

Zhai

Zhang

Song

2018

J of Physical Organic Chem

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“…See the right panel in Figure 3 for a comparison of the eigenvalue bounds obtained using m i instead of v i in the rightmost inequality in (9). We can see that the inner bounds Algorithm 1 Homo and lumo estimates obtained using information extracted from SP2…”

Section: Homo and Lumo Eigenvalue Estimatesmentioning

confidence: 91%

“…[4][5][6][7][8][9] The computation of the homo and lumo orbitals of a given Fock/Kohn-Sham matrix for large systems is of particular interest.…”

Section: Introductionmentioning

confidence: 99%

On-the-Fly Computation of Frontal Orbitals in Density Matrix Expansions

Kruchinina

Rudberg

Rubensson

2017

J. Chem. Theory Comput.

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Linear scaling density matrix methods typically do not provide individual eigenvectors and eigenvalues of the Fock/Kohn-Sham matrix, so additional work has to be performed if they are needed. Spectral transformation techniques facilitate computation of frontal (homo and lumo) molecular orbitals. In the purify-shift-and-square method the convergence of iterative eigenvalue solvers is improved by combining recursive density matrix expansion with the folded spectrum method [J. Chem. Phys. 128, 176101 (2008)]. However, the location of the shift in the folded spectrum method and the iteration of the recursive expansion selected for eigenpair computation may have a significant influence on the iterative eigenvalue solver performance and eigenvector accuracy. In this work, we make use of recent homo and lumo eigenvalue estimates [SIAM J. Sci. Comput. 36, B147 (2014)] for selecting shift and iteration such that homo and lumo orbitals can be computed in a small fraction of the total recursive expansion time and with sufficient accuracy. We illustrate our method by performing self-consistent field calculations for large scale systems.

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“…Furthermore, some molecules are highly sensitive to the change in the microenvironments, based on which Sytnik et al reported how the ESIPT chromophores can be used in the study of protein conformations and binding site polarity . Indeed, a lot of spectroscopic techniques were applied to study the ESIPT process in recent years, while the studies about ESIPT still have numerous challenges. That is to say, although lots of endeavors have been dedicated, the intrinsic complicated properties of physics and chemistry are still confused, for example, nuclear rearrangement, formation or cleavage of hydrogen bond wires, variations of excited state hydrogen bond, and so on.…”

Section: Introductionmentioning

confidence: 99%

Solvent controlling excited state proton transfer reaction in quinoline/isoquinoline‐pyrazole isomer QP‐I: A theoretical study

Yang

Zhao

et al. 2017

J of Physical Organic Chem

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In this present work, we theoretically study the excited state intramolecular proton transfer (ESIPT) mechanism about a quinoline/isoquinoline‐pyrazole isomer QP‐I system. Compared with previous experimental results, our calculated results reappear previous data, which further confirm the theoretical level we used is reasonable. We mainly adopt 2 kinds of solvents (nonpolar cyclohexane and polar acetonitrile) to explore solvents effects on this system. Through reduced density gradient (RDG) function, the intramolecular hydrogen bond N1─H2···N3 has been confirmed existing in both S0 and S1 states, although the distance between H2 and N3 is not short. In addition, the strengthening N1─H2···N3 in the S1 state provides possibility for ESIPT. Explorations about charge redistribution reveal the trend of ESIPT, and frontier orbital gap reflects the reactivity in polar and nonpolar solvents. The constructing potential energy curves reveal that potential energy barriers could be controlled and regulated by solvent polarity.

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A DFT/TDDFT investigation of the excited state proton transfer reaction of fisetin chromophore

Cited by 33 publications

References 71 publications

A theoretical study on the ESPT mechanism for a novel Bis‐HPBT fluorophore

A theoretical study on the ESPT mechanism for a novel Bis‐HPBT fluorophore

On-the-Fly Computation of Frontal Orbitals in Density Matrix Expansions

Solvent controlling excited state proton transfer reaction in quinoline/isoquinoline‐pyrazole isomer QP‐I: A theoretical study

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