Computational and Theoretical Chemistry最新文献_第7页

Revealing the crucial role of dissociated product NO2 in RDX catalyzed by metal oxides: A combined DFT and experimental study 揭示解离产物NO2在金属氧化物催化RDX中的关键作用：DFT和实验相结合的研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-12-26 DOI: 10.1016/j.comptc.2025.115645

Xiurong Yang , Jia Dang , Chi Zhang , Bo Liu , Haixia Ma

Metal oxides are widely used as combustion catalysts in propellants to promote the decomposition of energetic materials (EMs). To elucidate the underlying catalytic mechanism and facilitate the screening of effective catalysts, we employed density functional theory (DFT) to study the interactions of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and its key decomposition product NO₂ with various metal oxides. The adsorption behavior was correlated with the thermal decomposition performance of RDX/metal oxide mixtures. While only slight bond stretching in RDX was observed upon adsorption, strong adsorption of NO₂ was found to correlate with enhanced decomposition rates and lower activation energy for RDX. This trend was further validated in RDX/composite metal oxides systems. Our findings suggest that NO₂ adsorption energy can serve as an efficient and practical factor for predicting the catalytic activity of metal oxides toward RDX decomposition.

金属氧化物被广泛用作推进剂的燃烧催化剂，以促进含能物质的分解。为了阐明催化机理，筛选有效催化剂，我们采用密度泛函理论（DFT）研究了六氢-1,3,5-三硝基-1,3,5-三嗪（RDX）及其关键分解产物NO2与多种金属氧化物的相互作用。吸附行为与RDX/金属氧化物混合物的热分解性能有关。吸附时，RDX的键只发生轻微的拉伸，而NO2的强吸附与RDX的分解速率提高和活化能降低有关。这一趋势在RDX/复合金属氧化物体系中得到了进一步验证。研究结果表明，NO2吸附能可作为预测金属氧化物对RDX分解的催化活性的有效且实用的因子。

引用次数: 0

CO oxidation on noble-metal-free niobium‑nickel monoxide anion under NO/CO Co-adsorption NO/CO共吸附下无贵金属铌镍阴离子上的CO氧化

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-12-29 DOI: 10.1016/j.comptc.2025.115651

Jumei Zhang , Ziheng Zhang , Menghan Zhao , Weiwei Chen , Jiao Wang , Jinghan Zou , Xiangtao Kong , Hua Xie , Hongjin Qiao

Carbon monoxide (CO) oxidation is pivotal for exhaust-gas purification. Ambient co-adsorbates nitrogen monoxide (NO) can significantly affect CO oxidation. Herein, a series of NbNiO(NO)(CO)_n⁻ (n = 1–6) clusters were investigated by density functional theory. A bridging-O structure is most favorable for n = 1–3, then a terminal-O structure becomes favored for n = 4–5, and finally a CO₂-tagged structure is most favorable for n = 6. NO preferentially adsorbs at niobium (Nb) site, promoting CO oxidation by mediating the NbO interactions. During the consecutive CO adsorption, NO acts as an electron donor, and the metal centers display complementary electron transfer behavior: Nb acts as an electron acceptor for n ≤ 3, then switches to an electron donor at n = 4–5, and finally acts as an electron acceptor at n = 6, whereas nickel (Ni) exhibits the opposite trend. These findings provide atomistic insights into CO oxidation over heteronuclear metal oxides under co-adsorption conditions.

一氧化碳（CO）氧化是废气净化的关键。环境共吸附一氧化氮（NO）对CO氧化有显著影响。本文利用密度泛函理论研究了一系列NbNiO(NO)(CO)n−(n = 1-6)簇。当n = 1-3时，桥接o型结构最有利，当n = 4-5时，末端o型结构最有利，当n = 6时，co2标记型结构最有利。NO优先吸附在铌（Nb）位点，通过介导NbO相互作用促进CO氧化。在连续CO吸附过程中，NO作为电子给体，金属中心表现出互补电子转移行为：Nb在n≤3时为电子受体，在n = 4-5时转变为电子给体，在n = 6时最终成为电子受体，而镍（Ni）则表现出相反的趋势。这些发现提供了CO在共吸附条件下在异核金属氧化物上氧化的原子性见解。

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引用次数: 0

Interactions between carbon nanotubes and pulmonary surfactant proteins: the role of interfacial water molecules 碳纳米管与肺表面活性剂蛋白之间的相互作用：界面水分子的作用

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-12-26 DOI: 10.1016/j.comptc.2025.115646

Bhushan Dharmadhikari , Peiqiao Wu , Prabir Patra

Understanding the molecular interactions between proteins and carbon nanotubes (CNTs) is critical for optimizing the function and stability of protein-CNT interfaces. In this work, we use all-atom molecular dynamics simulations to examine how SP-B and SP-C adsorb onto an armchair (6,6) single-walled carbon nanotube (SWCNT) and how interfacial water influences this process. The two proteins follow distinct adsorption pathways: SP-B reaches stable contact with the nanotube within ∼2.5 ns, whereas SP-C requires ∼15 ns. Residue-level analysis shows that SP-B engages the surface through localized interactions, including π–π stacking involving its N-terminal phenylalanine (PHE-SWCNT), whereas SP-C forms more extended hydrophobic contacts along its longer α-helix, including CH–π interactions involving aliphatic and proline side chains with the SWCNT surface. The hydration environment also differs significantly. SP-B maintains a relatively stable hydration shell and forms more frequent protein-water hydrogen bonds, whereas SP-C exhibits intermittent “dry” interfacial states as it spreads over the nanotube. These dehydration events correlate with a secondary stabilization in its van der Waals interaction energy later in the trajectory. Taken together, the results show that the intrinsic structural features of SP-B and SP-C give rise to different adsorption dynamics and interfacial hydration responses. These findings help clarify how the molecular environment governs protein behavior at the nanoscale, informing the development of more effective protein-CNT biosensors.

了解蛋白质与碳纳米管（CNTs）之间的分子相互作用对于优化蛋白质-碳纳米管界面的功能和稳定性至关重要。在这项工作中，我们使用全原子分子动力学模拟来研究SP-B和SP-C如何吸附到扶手椅（6,6）单壁碳纳米管（SWCNT）上，以及界面水如何影响这一过程。这两种蛋白质遵循不同的吸附途径：SP-B在~ 2.5 ns内与纳米管稳定接触，而SP-C则需要~ 15 ns。残基水平分析表明，SP-B通过局部相互作用与SWCNT表面接触，包括涉及其n端苯丙氨酸（PHE-SWCNT）的π -π堆积，而SP-C沿着其较长的α-螺旋形成更多的疏水接触，包括涉及脂肪和脯氨酸侧链的CH -π与SWCNT表面的相互作用。水化环境也有很大的不同。SP-B保持相对稳定的水合外壳，形成更频繁的蛋白质-水氢键，而SP-C在纳米管上扩散时表现出间歇性的“干”界面状态。这些脱水事件与轨道后期范德华相互作用能的二次稳定有关。综上所述，SP-B和SP-C的固有结构特征导致了不同的吸附动力学和界面水化反应。这些发现有助于阐明分子环境如何在纳米尺度上控制蛋白质行为，为开发更有效的蛋白质碳纳米管生物传感器提供信息。

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引用次数: 0

Tuning of π-spacer engineering in D–π–A organic dyes for dye-sensitized solar cells: DFT/TD-DFT insights into enhanced optoelectronic and charge-transport properties 用于染料敏化太阳能电池的D -π-A有机染料中π-间隔层工程的调谐：DFT/TD-DFT对增强光电和电荷输运性质的见解

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-12-29 DOI: 10.1016/j.comptc.2025.115643

Ananta Panigrahi, Prabhat K. Sahu

This study presents a series of novel D–π–A organic dyes (1 A–4H) designed for dye-sensitized solar cells (DSSCs) using DFT and TD-DFT at 6–31 + G* level. Incorporating donor groups (amino, dimethylamine, methoxy, diphenylamine), fused thiophene and Thiazolo[5,4-d] thiazole π-spacers, and acceptors like –NO₂, –CN, and cyanoacrylic acid (CAA), the dyes are analyzed for optoelectronic performance. CAA-based dyes show enhanced intramolecular charge transfer, red-shifted absorption, and higher molar extinction coefficients. Dyes 1F, 1H, 4F, and 4H exhibit broader absorption bands, higher light-harvesting efficiency (up to 96.17 %), lower chemical hardness, and stronger electron injection driving force. Their large vertical dipole moments and increased conduction band electron population support superior photovoltaic performance. The computed results also support with favourable ionization energy, electron affinity, and reorganization energies. These findings highlight 1F, 1H, 4F, and 4H dyes for high-efficiency DSSC applications, warranting further experimental validation.

本研究利用DFT和TD-DFT在6-31 + G*水平上设计了一系列用于染料敏化太阳能电池（DSSCs）的新型D -π-A有机染料（1 a - 4h）。结合给基（氨基、二甲胺、甲氧基、二苯胺）、融合噻吩和噻唑[5,4-d]噻唑π-间隔基团以及受体（-NO₂、-CN、氰丙烯酸（CAA）），对染料进行了光电性能分析。caa基染料表现出增强的分子内电荷转移、红移吸收和更高的摩尔消光系数。染料1F、1H、4F和4H具有较宽的吸收带、较高的光收集效率（可达96.17%）、较低的化学硬度和较强的电子注入驱动力。它们大的垂直偶极矩和增加的导带电子居群支持优越的光伏性能。计算结果也支持有利的电离能、电子亲和能和重组能。这些发现突出了1F、1H、4F和4H染料在高效DSSC中的应用，需要进一步的实验验证。

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引用次数: 0

Hydrogen storage in second-row transition metal-decorated phosphorene nanoflakes: A DFT investigation 第二行过渡金属修饰磷烯纳米片中的储氢：DFT研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2026-01-01 DOI: 10.1016/j.comptc.2025.115656

Cesar Gabriel Vera de la Garza, Wilmer Esteban Vallejo Narvaez. Serguei Fomine

The hydrogen storage capacity of second-row transition-metal-decorated phosphorene nanoflakes (NFs) was investigated theoretically using the wB97M-D4/def2-TZVP(−f) level of theory. All second-row transition metals were found to form stable complexes with the phosphorene NFs. Among the series, NFs decorated with Mo, W, and Nb formed exergonic complexes with molecular hydrogen, with each metal atom capable of binding up to three H₂ molecules. The calculated Gibbs free binding energies ranged from −24.34 kcal/mol for the P–W–H₂ complex to 22.94 kcal/mol for the P–Y–H₂ complex. These complexes form without a significant activation energy barrier and involve partial dissociation of the HH bond. In specific cases, such as with W, Nb, and Mo, the binding mechanism involves hydride formation. Ab initio molecular dynamics simulations revealed a dynamic equilibrium between physisorption and chemisorption of H₂ molecules. The theoretical highest hydrogen storage capacities, approximately 2.73–2.77 wt%, were exhibited by Mo, W, and Nb.

采用wB97M-D4/def2-TZVP（−f）理论研究了第二行过渡金属修饰磷烯纳米片（NFs）的储氢能力。所有第二行过渡金属均与磷烯形成稳定的配合物。在这一系列中，以Mo、W和Nb修饰的NFs与分子氢形成了助能配合物，每个金属原子能够结合多达3个H₂分子。计算得到的吉布斯自由结合能从P-W-H2络合物的−24.34 kcal/mol到P-Y-H2络合物的22.94 kcal/mol不等。这些配合物的形成没有明显的活化能屏障，并涉及HH键的部分解离。在特定情况下，如W、Nb和Mo，结合机制涉及氢化物的形成。从头算分子动力学模拟揭示了H2分子的物理吸附和化学吸附之间的动态平衡。Mo、W和Nb的理论储氢量最高，约为2.73-2.77 wt%。

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引用次数: 0

Towards structure-property prediction in DyF3 nanoclusters DyF3纳米团簇结构-性能预测研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2026-01-02 DOI: 10.1016/j.comptc.2026.115657

Regina M. Burganova , Zafari Umar , Ilya V. Chepkasov , Hayk Zakaryan , Irina I. Piyanzina

Rare-earth trifluoride nanoparticles attract increasing attention due to their potential use in biomedical applications and spintronics, where understanding the correlation between structure and magnetic properties is crucial. However, experimental determination of these properties at the nanoscale remains challenging. In this work, the structures and magnetic characteristics of (DyF

_{3}

)

_{n}

(

n = 1

–10) nanoclusters were predicted and analyzed using an evolutionary algorithm combined with density functional theory. This study reveals how nanoclusters evolve structurally from symmetric monomers (C

_{3 v}

) to less symmetric larger clusters (C₁), with Dy-F bonds (2.02–2.96 Å), Dy-Dy distances (3.43–8.42 Å), and coordination numbers increasing from 3 to 8. Notably, magnetic moments grow with size, peaking near

\approx 45 μ_{B}

at

n = 10

, while spin compensation emerges at

n = 7

. Incorporating spin–orbit coupling highlights significant magnetic anisotropy energies up to 245 meV. Additionally, solvent effects provide substantial stabilization (

- 2.8

to

- 8.2

eV). These findings uniquely link structural changes to size-dependent magnetic properties, advancing predictive design of rare-earth fluoride nanomaterials.

三氟化稀土纳米颗粒由于其在生物医学和自旋电子学方面的潜在用途而越来越受到关注，在这些领域，了解结构和磁性之间的相关性至关重要。然而，在纳米尺度上对这些特性的实验测定仍然具有挑战性。本文采用进化算法结合密度泛函理论对（DyF3）n （n= 1-10）纳米团簇的结构和磁性进行了预测和分析。这项研究揭示了纳米团簇是如何从对称单体（C3v）进化到不对称的大团簇（C1）的，其中Dy-F键（2.02-2.96 Å）， Dy-Dy距离（3.43-8.42 Å），配位数从3增加到8。值得注意的是，磁矩随尺寸增大而增大，在n=10时磁矩在≈45μB附近达到峰值，而自旋补偿在n=7时出现。结合自旋轨道耦合突出了显著的磁各向异性能量，最高可达245mev。此外，溶剂效应提供了大量的稳定性（−2.8至−8.2 eV）。这些发现独特地将结构变化与尺寸相关的磁性联系起来，推进了稀土氟化物纳米材料的预测设计。

{"title":"Towards structure-property prediction in DyF3 nanoclusters","authors":"Regina M. Burganova , Zafari Umar , Ilya V. Chepkasov , Hayk Zakaryan , Irina I. Piyanzina","doi":"10.1016/j.comptc.2026.115657","DOIUrl":"10.1016/j.comptc.2026.115657","url":null,"abstract":"<div><div>Rare-earth trifluoride nanoparticles attract increasing attention due to their potential use in biomedical applications and spintronics, where understanding the correlation between structure and magnetic properties is crucial. However, experimental determination of these properties at the nanoscale remains challenging. In this work, the structures and magnetic characteristics of (DyF<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span>)<span><math><msub><mrow></mrow><mrow><mi>n</mi></mrow></msub></math></span> (<span><math><mrow><mi>n</mi><mo>=</mo><mn>1</mn></mrow></math></span>–10) nanoclusters were predicted and analyzed using an evolutionary algorithm combined with density functional theory. This study reveals how nanoclusters evolve structurally from symmetric monomers (C<span><math><msub><mrow></mrow><mrow><mn>3</mn><mi>v</mi></mrow></msub></math></span>) to less symmetric larger clusters (C<sub>1</sub>), with Dy-F bonds (2.02–2.96Å), Dy-Dy distances (3.43–8.42Å), and coordination numbers increasing from 3 to 8. Notably, magnetic moments grow with size, peaking near <span><math><mrow><mo>≈</mo><mn>45</mn><msub><mrow><mi>μ</mi></mrow><mrow><mi>B</mi></mrow></msub></mrow></math></span> at <span><math><mrow><mi>n</mi><mo>=</mo><mn>10</mn></mrow></math></span>, while spin compensation emerges at <span><math><mrow><mi>n</mi><mo>=</mo><mn>7</mn></mrow></math></span>. Incorporating spin–orbit coupling highlights significant magnetic anisotropy energies up to 245meV. Additionally, solvent effects provide substantial stabilization (<span><math><mrow><mo>−</mo><mn>2</mn><mo>.</mo><mn>8</mn></mrow></math></span> to <span><math><mrow><mo>−</mo><mn>8</mn><mo>.</mo><mn>2</mn></mrow></math></span> eV). These findings uniquely link structural changes to size-dependent magnetic properties, advancing predictive design of rare-earth fluoride nanomaterials.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115657"},"PeriodicalIF":3.0,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Saturation of magnetic exchange coupling with increasing cumulene coupler length in diarylmethyl diradicals 二芳基甲基二自由基中随累积烯偶联剂长度增加磁交换偶联的饱和

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-12-10 DOI: 10.1016/j.comptc.2025.115631

Muskan , Chumuiria Debbarma , Anirban Misra , Suranjan Shil

We have computationally designed nine diarylmethyl diradicals to understand the increasing trend of magnetic exchange coupling constant with the cumulene length. We have computed the magnetic exchange coupling constant with four different DFT functionals namely B3LYP, MN12SX, M06L and BP86 to check the consistency of the results. The molecular orbital analysis and their energy gap have also been studied. The bond length alternation increases with an increase in the length of the coupler. This suggests a clear shift in the molecule's electronic distribution with the increase in the cumulene length due to the interaction of the radical centers and the cumulene. All the functionals give consistent ferromagnetic interactions for the designed diradicals. After a certain length of the cumulene coupler the magnetic exchange coupling constant of the diradicals reached a saturation point. The MO analysis shows that the saturation of magnetic exchange comes from the reduced helical nature of LUMO.

我们计算设计了9个二芳基甲基二自由基，以了解磁交换偶联常数随积云长度的增加趋势。我们用四种不同的DFT泛函B3LYP， MN12SX， M06L和BP86计算了磁交换耦合常数，以检查结果的一致性。本文还研究了分子轨道分析及其能隙。键长交替随着耦合器长度的增加而增加。这表明，由于自由基中心与积云烯的相互作用，分子的电子分布随着积云烯长度的增加而发生明显的变化。所有的官能团对所设计的双基具有一致的铁磁相互作用。经过一定长度的积云耦合后，双自由基的磁交换耦合常数达到饱和点。MO分析表明，磁交换的饱和来自于LUMO的降低的螺旋性质。

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 : 2026-02-01 Epub 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

Exploration of the dissolution-separation characteristics of R1234yf with PVE68 and PAG100 lubricating oils R1234yf与PVE68和PAG100润滑油的溶分离特性探讨

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-12-16 DOI: 10.1016/j.comptc.2025.115635

Yao Pan, Wei Zhang, Zhao Yang, Yanfeng Zhao, Shuping Zhang, Yong Zhang

This study employs molecular dynamics simulations to investigate phase separation in mixtures of R1234yf-PVE68 and R1234yf-PAG100. Analyzing molecular clusters reveals that both temperature and concentration play a critical role in influencing phase behavior. In the case of R1234yf-PVE68, higher temperatures increase the

E_{vdW - SR}

and

E_{Disp - corr .}

forces between PVE68 molecules, thereby promoting phase separation. At low temperatures, the content of PVE68 governs the size of molecular aggregates, while at elevated temperatures, thermal motion predominates. In the case of R1234yf-PAG100, heating enhances intramolecular

E_{vdW}

interactions, reducing

E_{vdW}

repulsion and thus facilitating phase separation. By utilizing cluster algorithms to quantify phase domains, this work extends the study of refrigerant-lubricant systems to more practical molecular contexts. The results suggest that temperature weakens intramolecular cohesion, while the mass fraction influences system energy through molecular reorganization. These findings provide a theoretical framework for designing optimized refrigerant-lubricant combinations.

本研究采用分子动力学模拟研究了R1234yf-PVE68和R1234yf-PAG100混合物的相分离。对分子簇的分析表明，温度和浓度对相行为的影响至关重要。对于R1234yf-PVE68，温度越高，EvdW−SR和EDisp−系数越高。PVE68分子之间的力，从而促进相分离。在低温下，PVE68的含量决定了分子聚集体的大小，而在高温下，热运动占主导地位。在R1234yf-PAG100的情况下，加热增强了分子内EvdW的相互作用，减少了EvdW的排斥，从而促进了相分离。通过利用聚类算法来量化相域，这项工作将制冷剂-润滑剂系统的研究扩展到更实际的分子环境中。结果表明，温度削弱了分子内聚，而质量分数通过分子重组影响体系能量。这些发现为设计优化的制冷剂-润滑剂组合提供了理论框架。

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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 : 2026-02-01 Epub 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