设计的基于对苯醌的定向离子液体的结构、电子和热力学性质：来自DFT-GD3和QTAIM†的见解

IF 3.2 3区工程技术 Q2 CHEMISTRY, PHYSICAL

Molecular Systems Design & Engineering Pub Date : 2024-10-10 DOI:10.1039/D4ME00119B

Hossein Roohi, Sajedeh Habibipour and Khatereh Ghauri

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引用次数: 0

摘要

本文在M06-2X/6-31++G（d,p）理论水平上研究了不同阴离子对所设计的对苯醌基阳离子液体[BTAD][A1-8]2 ([BTAD]2+ = [p- c6o2 （N3H2)2]2+和A1-8 = [CH3CO2]−、[CF3CO2]−、[N(CN)2]−、[CF3SO3]−、[ClO4]−、[BF4]−、[NTf2]−和[PF6]−）的理化性质的影响。利用色散校正后的M06-2X-GD3、B2PLYP-GD3和mPW2PLYP-GD2泛函计算了校正后的相互作用能。考察了气体和溶剂介质中的热力学相互作用能、结构参数、静电势图、原子自然电荷、电荷转移（CT）、电子密度特性、阳极和阴极极限电位（VAL和VCL）、电化学窗口（ECW）、酸度（ΔpKa1和ΔpKa2）和还原梯度密度图（RGD）。基于修正后的相互作用能，[BTAD][A1-8]2配合物在各理论层次上的稳定顺序为[BTAD][CH3CO2]2 >；[BTAD] [CF3CO2] 2比;[BTAD] [N (CN) 2) 2比;[BTAD] [CF3SO3] 2比;[BTAD] [ClO4] 2比;[BTAD] [BF4] 2比;[BTAD] [NTf2] 2比;[BTAD] PF6 2。计算出的[BTAD][A3-8]2的ECW在4.5 ~ 7.5 V之间，表明这些il在电化学器件中可以替代目前使用的基于有机分子溶剂的电解质溶液。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

The structural, electronic and thermodynamic properties of the designed p-benzoquinone based dicationic ionic liquids: insight from DFT–GD3 and QTAIM†

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The structural, electronic and thermodynamic properties of the designed p-benzoquinone based dicationic ionic liquids: insight from DFT–GD3 and QTAIM†

In this work, the impact of various anions on the physicochemical properties of the designed p-benzoquinone-based dicationic ionic liquids [BTAD][A1–8]₂ ([BTAD]²⁺ = [p-C₆O₂(N₃H₂)₂]²⁺ and A1–8 = [CH₃CO₂]⁻, [CF₃CO₂]⁻, [N(CN)₂]⁻, [CF₃SO₃]⁻, [ClO₄]⁻, [BF₄]⁻, [NTf₂]⁻ and [PF₆]⁻) was investigated at the M06-2X/6-31++G(d,p) level of theory in the gas phase and solvent media. Besides, dispersion-corrected M06-2X-GD3, B2PLYP-GD3 and mPW2PLYP-GD2 functionals were employed to calculate the corrected interaction energies. The thermodynamic interaction energies in gas and solvent media, structural parameters, electrostatic potential maps, natural charge of atoms, charge transfer (CT), electron density properties, potentials of the anodic and cathodic limits (V_AL and V_CL), electrochemical windows (ECW), acidity (ΔpK_a1 and ΔpK_a2) and reduced gradient density plots (RGD) were examined. Based on the corrected interaction energies, the stability order of [BTAD][A1–8]₂ complexes at all levels of theory is [BTAD][CH₃CO₂]₂ > [BTAD][CF₃CO₂]₂ > [BTAD][N(CN)₂]₂ > [BTAD][CF₃SO₃]₂ > [BTAD][ClO₄]₂ > [BTAD][BF₄]₂ > [BTAD][NTf₂]₂ > [BTAD][PF₆]₂. The calculated ECW of [BTAD][A3–8]₂ is in the range of 4.5 to 7.5 V, demonstrating that these ILs can be promising candidates for the substitution of currently used electrolyte solutions based on organic molecular solvents in electrochemical devices.

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来源期刊

Molecular Systems Design & Engineering Engineering-Biomedical Engineering

CiteScore

6.40

自引率

2.80%

发文量

144

期刊介绍： Molecular Systems Design & Engineering provides a hub for cutting-edge research into how understanding of molecular properties, behaviour and interactions can be used to design and assemble better materials, systems, and processes to achieve specific functions. These may have applications of technological significance and help address global challenges.