Effect of the mixture composition of Acetonitrile/Benzene on excited state intramolecular proton transfer in 3-hydroxyflavone, theoretical insights: QTAIM, NBO, NLO behavior, thermodynamic and kinetic aspects

IF 2.7 4区生物学 Q2 BIOCHEMICAL RESEARCH METHODS

Journal of molecular graphics & modelling Pub Date : 2025-03-03 DOI:10.1016/j.jmgm.2025.109001

Fatma Zohra Imene Yeddou , Mohamed Ali Benmensour , Anissa Amar

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Abstract

The effect of the Acetonitrile/Benzene mixture composition on excited state intramolecular proton transfer in 3-hydroxyflavone (3HF) was studied by means of density functional theory (DFT) and time-dependent DFT (TDDFT). The static dielectric constant ε_m is considered as a polarity parameter to characterize the composition of the two mixed solvents. We used the B3LYP/6-31G(d) level of theory for all the calculations of various properties (structural, electronic, spectroscopic, photophysical) in both ground and excited states. Our initial findings show that the mixture composition has a negligible effect on the geometry parameters. The computation of the maximum absorption and fluorescence wavelengths for 3HF and its tautomer correlates well with their corresponding experimental counterparts. The QTAIM and NBO tools were employed to estimate the strength of intramolecular hydrogen bond IHB. It reveals that E_HB is weakened with the increase of ε_m, due to the existence of electrostatic interactions. The title molecule is prone to exhibit remarkable NLO response. Secondly, the kinetic and thermodynamic outcomes, together with all former results, strongly support the occurrence of ESIPT phenomenon. Meanwhile, they also highlight the limits of PCM model in accurately describing solute-solvent interactions. Finally, the estimated ESIPT time is very close to the experimental values, which validates our level of theory.

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乙腈/苯混合物组成对3-羟基黄酮分子内激发态质子转移的影响，理论见解：QTAIM， NBO， NLO行为，热力学和动力学方面

采用密度泛函理论（DFT）和时变泛函理论（TDDFT）研究了乙腈/苯混合物组成对3-羟基黄酮（3HF）分子内激发态质子转移的影响。采用静态介电常数εm作为表征两种混合溶剂组成的极性参数。我们使用B3LYP/6-31G(d)理论水平计算了基态和激发态下的各种性质（结构、电子、光谱、光物理）。我们的初步研究结果表明，混合成分对几何参数的影响可以忽略不计。3HF及其互变异构体的最大吸收波长和荧光波长的计算结果与相应的实验结果相吻合。采用QTAIM和NBO工具估计分子内氢键IHB的强度。结果表明，由于静电相互作用的存在，EHB随着εm的增大而减弱。标题分子容易表现出显著的NLO反应。其次，动力学和热力学结果与前面的所有结果一起有力地支持了ESIPT现象的发生。同时，他们也强调了PCM模型在准确描述溶质-溶剂相互作用方面的局限性。最后，估计的ESIPT时间与实验值非常接近，验证了我们的理论水平。

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来源期刊

Journal of molecular graphics & modelling 生物-计算机：跨学科应用

CiteScore

5.50

自引率

6.90%

发文量

216

审稿时长

35 days

期刊介绍： The Journal of Molecular Graphics and Modelling is devoted to the publication of papers on the uses of computers in theoretical investigations of molecular structure, function, interaction, and design. The scope of the journal includes all aspects of molecular modeling and computational chemistry, including, for instance, the study of molecular shape and properties, molecular simulations, protein and polymer engineering, drug design, materials design, structure-activity and structure-property relationships, database mining, and compound library design. As a primary research journal, JMGM seeks to bring new knowledge to the attention of our readers. As such, submissions to the journal need to not only report results, but must draw conclusions and explore implications of the work presented. Authors are strongly encouraged to bear this in mind when preparing manuscripts. Routine applications of standard modelling approaches, providing only very limited new scientific insight, will not meet our criteria for publication. Reproducibility of reported calculations is an important issue. Wherever possible, we urge authors to enhance their papers with Supplementary Data, for example, in QSAR studies machine-readable versions of molecular datasets or in the development of new force-field parameters versions of the topology and force field parameter files. Routine applications of existing methods that do not lead to genuinely new insight will not be considered.