Computational and Theoretical Chemistry最新文献_第5页

Engineering ORR electrocatalytic performance of single metal site by halogen ligand modification: A first principles perspective 卤素配体修饰单金属位点的工程ORR电催化性能：第一性原理观点

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-05 DOI: 10.1016/j.comptc.2025.115627

Shaoqiang Wei , Lei Li , Mengjiao Wu , Huanhuan Wu , Mengqi Yang , Min Zhang

Identifying the well-recognized active sites of single-atom catalysts to modulate the oxygen reduction reaction (ORR) catalytic activity and product selectivity is a challenging problem. In this work, using density functional theory (DFT) calculations, we conducted a systematic study for 3d metal and nitrogen co-doped graphene single-atom catalysts (MN₄), as well as the MN₄ modified by halogen ligand X (MN₄–X). The results indicate that all catalysts, except for ZnN₄ and ZnN₄–X, are thermodynamically and electrochemically stable. The ORR follows the 4e⁻ pathway on Cr/Mn/Fe/CoN₄ and Cr/Mn/Fe/CoN₄–X, while Ni/CuN₄ and Ni/CuN₄–X prefer the 2e⁻ ORR pathway. The X ligand can effectively change the electronic structure of M active site to regulate the adsorption strength for reaction intermediates, thus enhancing the ORR catalytic activity. Notably, CoN₄–Br/I have the lowest 4e⁻ ORR overpotential of about 0.24 V and exhibit superior catalytic activity, significantly outperforming pure Pt catalysts. However, NiN₄–F and CuN₄ respectively with the overpotential of 0.08 and 0.03 V display the excellent 2e⁻ ORR catalytic activity. Furthermore, the O₂ adsorption energy, Bader charge transfer of M atoms, ΔG_⁎OH, and ΔG_⁎OOH were demonstrated to be the descriptors for evaluating the ORR activity and product selectivity. This study provides valuable insights for the design of highly efficient ORR catalysts.

确定已知的单原子催化剂活性位点来调节氧还原反应（ORR）的催化活性和产物选择性是一个具有挑战性的问题。本文利用密度泛函理论（DFT）计算，系统研究了三维金属和氮共掺杂石墨烯单原子催化剂（MN4），以及卤素配体X修饰的MN4 （MN4 - X）。结果表明，除ZnN4和ZnN4 - x外，其余催化剂均具有良好的热力学和电化学稳定性。Cr/Mn/Fe/CoN4和Cr/Mn/Fe/CoN4 - x的ORR倾向于4e−途径，而Ni/CuN4和Ni/CuN4 - x的ORR倾向于2e−ORR途径。X配体可以有效改变M活性位点的电子结构，调节对反应中间体的吸附强度，从而提高ORR催化活性。值得注意的是，CoN4-Br /I具有最低的4e−ORR过电位，约为0.24 V，并表现出优异的催化活性，明显优于纯Pt催化剂。而过电位分别为0.08 V和0.03 V的NiN4-F和CuN4则表现出优异的2e - ORR催化活性。此外，O2吸附能、M原子的Bader电荷转移、ΔG OH和ΔG OOH被证明是评价ORR活性和产物选择性的描述符。该研究为高效ORR催化剂的设计提供了有价值的见解。

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引用次数: 0

Crystallographic site-dependent spintronic properties of CoMnTe/CdS(001) interfaces: A first-principles study comte /CdS（001）界面的晶体位依赖自旋电子特性：第一性原理研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-04 DOI: 10.1016/j.comptc.2025.115621

Abdelkrim Kessai , Nacir Guechi , Mustafa Kurban , Hakim Baaziz , Abdelhamid Layadi

We present a first-principles investigation, based on the pseudopotential plane-wave (PP-PW) method, of the CoMnTe/CdS(001) interfaces, focusing on the role of crystallographic site configurations—top (t), bridge (b), and hollow (h)—in determining their spintronic properties. These properties include structural stability, work function, half-metallicity, spin polarization, spin and charge populations, adhesion energy, and interfacial bonding. MnTe-terminated surface preserves the half-metallicity of bulk CoMnTe, while Co-terminated surface loses this feature due to created minority spin surface states (53 %) at the Fermi level (E_F). Electronic and magnetic modifications are largely confined to the first two layers at the surface, where significant increase in Co and Mn magnetic moments are observed. Among twelve distinct interface configurations, only two—Co (b)/S and Mn (t)Te(h)/Cd—retain 100 % spin polarization at E_F, with adhesion energies of 3.12 J/m² and 0.51 J/m², respectively. Hirshfeld charge and spin population analyses reveal covalent bonding between Co and S, and ionic bonding between Mn and Cd, along with a weak induced magnetic moment (−0.05 μ_B) on the Cd-terminated side. These findings identify promising interface configurations for spintronic device applications.

我们提出了基于伪势平面波（PP-PW）方法的comte /CdS（001）界面的第一性原理研究，重点关注晶体位置配置-顶部(t)，桥(b)和空心(h) -在确定其自旋电子性质中的作用。这些性质包括结构稳定性、功函数、半金属性、自旋极化、自旋和电荷居群、粘附能和界面键合。mnte端表面保留了本体comte的半金属性，而co端表面由于在费米能级（EF）产生了少数自旋表面态（53%）而失去了这一特征。电子和磁性修饰主要局限于表面的前两层，在那里观察到Co和Mn磁矩的显著增加。在12种不同的界面构型中，只有2 - co (b)/S和Mn (t)Te(h)/ cd在EF下保持100%的自旋极化，粘附能分别为3.12 J/m2和0.51 J/m2。Hirshfeld电荷和自旋占比分析表明，Co和S之间存在共价键，Mn和Cd之间存在离子键，Cd端存在弱磁矩（−0.05 μB）。这些发现确定了自旋电子器件应用的有前途的界面配置。

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引用次数: 0

Effect of tube radius on the adsorption of chlorothalonil on single-walled carbon and boron nitride nanotubes surfaces: A theoretical study for environmental remediation 管半径对碳纳米管和氮化硼纳米管表面吸附百菌清的影响：环境修复的理论研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-04 DOI: 10.1016/j.comptc.2025.115626

Francisco Gleidson de S. Ferreira , Caio V.C. Ribeiro da Silva , Silvete Guerini , Kleuton A.L. Lima , Douglas Soares Galvão , José Milton Elias de Matos , Alexandre Araujo de Souza

The interaction of the pollutant chlorothalonil (CLT) with single-walled carbon nanotubes (CNTs) and boron nitride nanotubes (BNNTs) was investigated using density functional theory (DFT) calculations with the SIESTA software. Structural, energetic, and electronic properties were analyzed to characterize the effects of the interaction on the nanotube surfaces. Adsorption energy increases with increasing nanotube radius, attributed to enhanced π–π stacking interactions. The results indicate that both CNTs and BNNTs can physically adsorb CLT, but BNNTs are more promising candidates for CLT detection and removal in contaminated environments. Nanotube radius strongly affects all electronic and energetic properties. Molecular dynamics simulations performed in GROMACS confirmed the stability of CLT adsorbed on CNT and BNNT surfaces in aqueous solution.

采用密度泛函理论（DFT）计算方法，利用SIESTA软件研究了污染物百菌清（CLT）与单壁碳纳米管（CNTs）和氮化硼纳米管（bnnt）的相互作用。分析了结构、能量和电子特性，以表征相互作用对纳米管表面的影响。吸附能随着纳米管半径的增加而增加，这是由于π -π堆积相互作用的增强。结果表明，碳纳米管和bnnt都可以物理吸附CLT，但bnnt更有希望在污染环境中检测和去除CLT。纳米管半径强烈影响所有电子和能量性质。在GROMACS中进行的分子动力学模拟证实了CLT在水溶液中吸附在碳纳米管和BNNT表面的稳定性。

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引用次数: 0

Study on the influence of functional groups on coal surface wettability based on density functional theory, gran canonica monte caro, and moecular dynamics 基于密度泛函理论、grcanonica monte caro和分子动力学的官能团对煤表面润湿性影响研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-03 DOI: 10.1016/j.comptc.2025.115622

Jinzhang Jia , Chaoyang Li , Peng Jia , Fengxiao Wang

To elucidate the wetting mechanisms of different functional groups at the molecular scale, this study systematically investigated the interaction mechanisms between 11 functional groups in coal and water using Density Functional Theory (DFT), Gran Canonica Monte Caro (GCMC), and Moecular Dynamics (MD) simulation methods. The study reveals that functional group polarity can be quantitatively distinguished by electrostatic potential maxima. As the sole bipolar functional group, the carboxyl group exhibits both strong donor and acceptor characteristics. It forms the strongest adsorption through C=O…H and O-H…O double hydrogen bonds, demonstrating superhydrophilicity. Front-line orbital analysis revealed that hydrophilic functional groups possess lower LUMO energy levels and higher electrophilic power, facilitating electron acceptance from water molecules. RDF analysis indicated that hydrophilic functional groups exhibit lower surface water molecule aggregation, promoting spreading. This study employs multiscale simulations to elucidate the mechanism by which functional groups influence coal wettability, providing precise theoretical foundations and design guidance for optimizing coal processing through surface functional group design.

为了在分子尺度上阐明不同官能团的润湿机理，本研究采用密度泛函理论（DFT）、Gran Canonica Monte Caro （GCMC）和分子动力学（MD）模拟方法系统研究了煤与水中11个官能团的相互作用机理。研究表明，可以通过静电势最大值定量地区分官能团极性。作为唯一的双极性官能团，羧基表现出强烈的供体和受体特征。通过C=O…H和O-H…O双氢键形成最强吸附，表现出超亲水性。前线轨道分析表明，亲水官能团具有较低的LUMO能级和较高的亲电能力，有利于从水分子中接受电子。RDF分析表明亲水性官能团表现出较低的地表水分子聚集，促进扩散。本研究通过多尺度模拟阐明了官能团对煤润湿性的影响机理，为通过表面官能团设计优化煤的加工提供了精确的理论依据和设计指导。

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引用次数: 0

Mechanism and kinetics of chlorothalonil reaction with atmospheric oxidants 百菌清与大气氧化剂反应机理及动力学

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-03 DOI: 10.1016/j.comptc.2025.115624

S.V. Thoshiba , L. Sandhiya , K. Senthilkumar

Chlorothalonil (CTN) is an organochlorine fungicide, widely used in agriculture and in protective coatings. CTN is categorized as a probable human carcinogen. In this work, reaction of CTN with atmospheric oxidants (•OH, •NO₃ and O₃) are studied using electronic structure calculations. Energy barrier for the reaction of CTN with •OH and •NO₃ lies in the range of 7–10 kcal/mol, while for O₃ initiated reactions the energy barrier is around 20 kcal/mol. At 298 K, the rate constant for the formation of CTN-OH and CTN-NO₃ adduct intermediates is 3.65 × 10⁻¹³ and 3.29 × 10⁻¹⁸ cm³molecule⁻¹s⁻¹, respectively. The •OH-initiated reactions are investigated in gas and aqueous phases. The subsequent reactions of CTN-OH adduct intermediates are studied in detail to identify the possible degradation products of CTN. Results from excited state calculations show that photolysis of CTN is unlikely. The results from toxicity assessment show that the CTN and its degradation products are harmful to aquatic organisms.

百菌清（CTN）是一种有机氯杀菌剂，广泛应用于农业和防护涂料。CTN被归类为可能的人类致癌物。本文采用电子结构计算方法研究了CTN与大气氧化剂（•OH、•NO3和O3）的反应。CTN与•OH和•NO3反应的能垒在7 ~ 10 kcal/mol之间，而O3引发反应的能垒在20 kcal/mol左右。在298 K下，CTN-OH和CTN-NO3加合产物的生成速率常数分别为3.65 × 10−13和3.29 × 10−18 cm3molecule - 1s−1。在气相和水相中研究了•oh引发的反应。详细研究了CTN- oh加合中间体的后续反应，以确定CTN可能的降解产物。激发态计算结果表明，CTN不可能发生光解。毒性评价结果表明，CTN及其降解产物对水生生物有害。

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引用次数: 0

Assessment of GFN-FF and GFN2-xTB methods for binding free energy calculations: Application to cucurbit[7]uril-cationic guest complexes GFN-FF和GFN2-xTB结合自由能计算方法的评估：在葫芦[7]脲-阳离子客体配合物中的应用

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-29 DOI: 10.1016/j.comptc.2025.115605

Wissam Helal

The performance of two cost-efficient computational methods, the semiempirical extended tight-binding GFN2-xTB and the GFN-FF force field, was assessed for predicting the binding free energies of cucurbit[7]uril host–guest complexes with a series of cationic ammonium guests. Binding energies were computed via the supermolecular approach and decomposed into gas-phase interaction, thermostatistical, and solvation components. Both methods reproduce the general energetic trends of experimental binding affinities, with GFN-FF yielding lower mean absolute errors and standard deviations. However, the GFN2-xTB geometries are consistently closer to high-level DFT reference structures. The results indicate that while GFN-FF offers substantial computational efficiency and acceptable accuracy for screening purposes, its apparent energetic agreement may arise partly from error cancellation rather than superior physical description. The study also highlights the limitations of the single-structure supermolecular approach, particularly for flexible host–guest systems, where conformational sampling are required for a quantitatively reliable description of binding thermodynamics.

评价了半经验扩展紧密结合GFN2-xTB和GFN-FF力场两种具有成本效益的计算方法在预测葫芦[7]- uril主客体配合物与一系列阳离子铵客体结合自由能方面的性能。通过超分子方法计算结合能，并将其分解为气相相互作用、热统计和溶剂化组分。两种方法都再现了实验结合亲和的一般能量趋势，GFN-FF产生更低的平均绝对误差和标准偏差。然而，GFN2-xTB几何形状始终更接近于高级DFT参考结构。结果表明，虽然GFN-FF为筛选目的提供了可观的计算效率和可接受的准确性，但其明显的能量一致性可能部分来自误差消除，而不是优越的物理描述。该研究还强调了单结构超分子方法的局限性，特别是对于灵活的主客体系统，其中需要进行构象采样以定量可靠地描述结合热力学。

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引用次数: 0

Correlation between the enthalpy of formation of gaseous atoms from elemental substances and the bond dissociation energy of homonuclear diatomic molecules: Exploratory perspectives on alternative classification schemes for chemical elements 元素物质形成气态原子的焓与同核双原子分子的键解离能之间的关系：对化学元素分类方案的探索

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-29 DOI: 10.1016/j.comptc.2025.115604

Marco Aurélio Cebim

This study introduces a novel framework for classifying chemical elements grounded in the correlation of energetic parameters associated with chemical bonding in elemental substances under standard conditions. The enthalpy of formation of gaseous atoms (

∆_{f} H^{o}

) and the bond dissociation energy (

BDE

) are employed to define a dimensionless quantity (

β = ∆_{f} H^{o} / BDE

). This parameter reflects the tendency of elements to form simple neutral molecules of the type

X_{n}

. Representative

β

values and other relevant properties are discussed throughout the manuscript. The chemical elements were represented in a scatter plot of

∆_{f} H^{o}

as a function of

BDE

, in which a wide separation between metals and nonmetals (and noble gases) is observed, with metalloids distributed between these two types of elements. Finally, a scatter plot is proposed relating the

β

parameter and electronegativity, in which the chemical elements appear grouped as metals, metalloids, and nonmetals without apparent ambiguity.

本研究提出了一种新的化学元素分类框架，该框架基于元素物质在标准条件下化学键相关的能量参数的相关性。用气态原子的形成焓（∆fHo）和键离解能（BDE）来定义一个无因次量（β=∆fHo/BDE）。该参数反映了元素形成Xn型简单中性分子的倾向。具有代表性的β值和其他相关性质在全文中都有讨论。化学元素以散点图（∆fHo）表示为BDE的函数，其中观察到金属和非金属（以及惰性气体）之间有很大的分离，类金属分布在这两种元素之间。最后，提出了β参数与电负性的散点图，其中化学元素按金属、类金属和非金属分组，没有明显的歧义。

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引用次数: 0

A systematic DFT study on the effects of oxygen vacancy concentration and site-dependence on polarization switching in HfO2 氧空位浓度和位依赖对HfO2中极化开关影响的系统DFT研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-29 DOI: 10.1016/j.comptc.2025.115603

Jiaying Shang, Minghui Kong, Qiankun Zhang

As HfO₂’s use in ferroelectrics has grown revolutionarily lately, and common oxygen vacancies in it have unclear polarization switching regulation mechanisms, investigating how their concentration and position affect HfO₂’s polarization switching matters for ferroelectric development. Based on density functional theory, a series of HfO₂ structures with different concentrations and positions of oxygen vacancies are constructed. The calculation results of formation energy show that the difficulty of forming oxygen vacancies is significantly related to the coordination environment and concentration. Through the CI-NEB method, the energy barrier is calculated, revealing that as the concentration of O vacancies increases, the entire energy barrier will gradually decrease. The energy barrier of HfO₂-V4-I can be reduced to 0.67 eV. This study clarifies the regulatory rules of oxygen vacancies on the polarization switching of HfO₂, providing a key theoretical basis for optimizing the performance of ferroelectric devices through defect engineering.

近年来，HfO₂在铁电体中的应用得到了革命性的发展，而其中常见的氧空位的极化开关调节机制尚不清楚，研究它们的浓度和位置如何影响HfO₂的极化开关对铁电体的发展具有重要意义。基于密度泛函理论，构建了一系列具有不同氧空位位置和不同浓度的HfO2结构。形成能的计算结果表明，氧空位的形成难易程度与配位环境和配位浓度有显著关系。通过CI-NEB方法计算了能势垒，发现随着O空位浓度的增加，整个能势垒会逐渐降低。HfO2-V4-I的能垒可以降低到0.67 eV。本研究阐明了氧空位对HfO2极化开关的调控规律，为通过缺陷工程优化铁电器件性能提供了关键的理论依据。

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引用次数: 0

Exploring the elusive catalytic role of water in the OH ＋ furan reaction 探索水在OH +呋喃反应中难以捉摸的催化作用

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-29 DOI: 10.1016/j.comptc.2025.115616

Joel Leitão Nascimento, Daniel Moura, Edivania Santana, Vitor H. Menezes da Silva, Tiago Vinicius Alves

A comprehensive understanding of how water vapor affects the OH-addition to furan is essential, as these reactions constitute one of the primary atmospheric degradation pathways. The ability of water to form highly stable two- and three-body complexes creates the possibility for modulating the reaction mechanism for furan degradation in the gas-phase, thus motivating us to carry out a systematic investigation of its elusive catalytic role on this process. To this end, Density Functional Theory (DFT) calculations have been performed, providing thirteen distinct water-assisted pathways computed. In addition, the canonical variational transition state theory with small-curvature tunneling (CVT/SCT), combined with the pre-equilibrium model (PEM), have been employed in order to compute termolecular and effective rate constants at different relative humidities. Overall, the results indicate that the catalytic effect of water, including contributions from H-abstraction is negligible, although its occurrence cannot be entirely ruled out under high-temperature conditions. Specifically, under tropospheric conditions, water-mediated OH-addition pathways are kinetically disfavored by more than three orders of magnitude compared to the gas-phase mechanism.

全面了解水蒸气如何影响oh加成呋喃是必要的，因为这些反应构成了主要的大气降解途径之一。水形成高度稳定的二体和三体配合物的能力创造了调节气相呋喃降解反应机制的可能性，因此促使我们对其在这一过程中难以捉摸的催化作用进行系统的研究。为此，密度泛函理论（DFT）进行了计算，提供了13种不同的水辅助路径计算。此外，为了计算不同相对湿度下的三分子速率常数和有效速率常数，本文还采用了带小曲率隧道的正则变分过渡态理论（CVT/SCT）和预平衡模型（PEM）相结合的方法。总的来说，结果表明水的催化作用，包括h萃取的贡献是可以忽略不计的，尽管在高温条件下不能完全排除它的发生。具体来说，在对流层条件下，与气相机制相比，水介导的oh加成途径在动力学上是不利的，超过三个数量级。

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引用次数: 0

Understanding the aqueous behavior of decanoic acid-based deep eutectic solvents via COSMO-RS and molecular simulations 通过cosmos - rs和分子模拟了解癸酸基深共晶溶剂的水行为

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-29 DOI: 10.1016/j.comptc.2025.115608

Samaneh Barani Pour , Behie Amirian , Leyla Bagheri , Jaber Jahanbin Sardroodi

Background

Deep eutectic solvents (DESs) based on decanoic acid have emerged as promising green solvents due to their biodegradability and tunable properties. However, their behavior in aqueous environments remains insufficiently understood, limiting their broader application in chemical processes.

Methods

COSMO-RS (Conductor-like Screening Model for Real Solvents) calculations, combined with molecular dynamics simulations, were employed to systematically investigate the intermolecular interactions, miscibility, and structural organization of decanoic acid–based deep eutectic solvents in the presence of water. A detailed analysis of thermodynamic descriptors, hydrogen-bonding patterns, and spatial distribution functions was conducted to elucidate the solvent behavior and molecular-level interaction mechanisms governing water – DES systems.

Significant findings

The results reveal non-ideal mixing behavior and highlight the critical role of hydrogen bonding and hydrophobic interactions in governing aqueous phase behavior. COSMO-RS predicted partial miscibility trends consistent with simulation results. These insights offer a theoretical foundation for designing water-compatible DES systems for sustainable chemical applications. The interactions between DES components and water molecules were systematically analyzed to understand the solvation effects, hydrogen bonding networks, and structural properties in varying hydration levels. This study examines key properties such as the combined distribution function, spatial distribution function, intermolecular hydrogen bond network, interaction energy, species orientation, density, and self-diffusion coefficients (D_self). Molecular dynamics simulations reveal that increasing the water mass fraction up to 50% weakens the interaction between DES components, significantly impacting their stability and solvation characteristics. These findings provide valuable insights into the behavior of hydrophobic DESs, contributing to their potential applications in pharmaceutical and green chemistry fields.

基于癸酸的深共晶溶剂（DESs）由于其可生物降解和可调的特性而成为一种很有前途的绿色溶剂。然而，它们在水环境中的行为仍然不够清楚，限制了它们在化学过程中的广泛应用。方法采用scosmos - rs（导体样筛选模型）计算和分子动力学模拟相结合的方法，系统地研究了十二酸基深共晶溶剂在水存在下的分子间相互作用、混相和结构组织。通过对热力学描述符、氢键模式和空间分布函数的详细分析，阐明了水- DES体系的溶剂行为和分子水平相互作用机制。结果揭示了非理想的混合行为，并强调了氢键和疏水相互作用在控制水相行为中的关键作用。cosmos - rs预测的部分混相趋势与模拟结果一致。这些见解为设计可持续化学应用的水兼容DES系统提供了理论基础。系统分析了DES组分与水分子之间的相互作用，以了解不同水化水平下的溶剂化效应、氢键网络和结构性质。本研究考察了复合分布函数、空间分布函数、分子间氢键网络、相互作用能、物种取向、密度和自扩散系数（Dself）等关键性质。分子动力学模拟表明，当水质量分数增加到50%时，DES组分之间的相互作用减弱，显著影响其稳定性和溶剂化特性。这些发现为研究疏水DESs的行为提供了有价值的见解，有助于其在制药和绿色化学领域的潜在应用。

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引用次数: 0