Computational and Theoretical Chemistry最新文献

Precise positioning of acceptor benzothiadiazole in D-(A)3 push-pull system to tailor the optoelectronic and photovoltaic performance: A DFT and TD-DFT study D-(A)3推挽系统中受体苯并噻二唑的精确定位以定制光电和光伏性能：DFT和TD-DFT研究

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-08-13 DOI: 10.1016/j.comptc.2026.116006

Pankaj Kumar Kushwaha, Prabhat Gautam, Sunil Kumar Srivastava

Push-pull π-conjugated small molecules have found extensive application in organic solar cells. The development of such molecular systems has been considered in a wide variety of pathways by altering the donor/acceptor units and π-linkers. In this work, three series of D-(A)₃ benzothiadiazole (BT) coupled push-pull systems; Series 1 (BT1-BT3), Series 2 (BT4-BT6), and Series 3 (BT7-BT9) were designed by precise positioning of the acceptor benzothiadiazole unit around the triphenylamine core, and systematically explored using density functional theory (DFT) to establish structure–property relationships. The impact of benzothiadiazole acceptor positioning across various permutations on the three phenyl arms of the triphenylamine was investigated in terms of structural and optoelectronic properties, as well as intramolecular charge-transfer behavior. In all three series, the acceptor benzothiadiazoles at the single arm of the triphenyamine (TPA) show remarkably reduced HOMO-LUMO energy gap, improved λ_max values, and high oscillator strength (f). Hole-electron localization and electronic excitation processes in the excited state were examined using Transition density matrix maps. The efficiency of these materials was determined by evaluating the photovoltaic parameters (V_OC, J_SC, and PCE). The photovoltaic parameters for devices with PC₇₁BM as acceptor in the device structure show significantly improved values for molecular systems in Series 3 compared to Series 1 and Series 2. It is observed that positioning multiple BT/CNBT acceptors on the triphenylamine arms, supplemented with π-spacer and CN-acceptor groups, is undoubtedly a potential strategy to enhance the performance of donor materials for OSC applications. The Series 3 system exhibits a strong push-pull mechanism, leading to a small optical band gap (1.24 eV), strong intramolecular charge transfer (ICT), and low reorganization energies. These properties contribute to an enhanced short-circuit current density (J_SC) ∼ 21.97 mA/cm², an open-circuit voltage (V_OC) ∼ 1.04 V, minimal energy loss (0.53 eV), and theoretical power conversion efficiency (PCE) up to ~15.66%.

推挽π共轭小分子在有机太阳能电池中有着广泛的应用。通过改变供体/受体单位和π-连接体，这种分子体系的发展被认为是多种途径。本研究采用三系D-(A)3苯并噻唑（BT）偶联推挽体系；系列1 （BT1-BT3）、系列2 （BT4-BT6）和系列3 （BT7-BT9）通过对受体苯并噻唑单元在三苯胺核心周围的精确定位进行设计，并利用密度泛函理论（DFT）系统探索建立构效关系。从结构、光电性质以及分子内电荷转移行为等方面研究了苯并噻唑受体不同排列对三苯胺三个苯基臂的影响。在这三个系列中，三苯胺（TPA）单臂上的受体苯并噻吩二唑表现出明显减小的HOMO-LUMO能隙，提高的λmax值和高的振荡强度(f)。利用跃迁密度矩阵图研究了激发态的空穴-电子局域化和电子激发过程。通过评估光伏参数（VOC， JSC和PCE）来确定这些材料的效率。在器件结构中以PC71BM为受体的器件的光伏参数显示，与系列1和系列2相比，系列3分子体系的数值有显著提高。结果表明，在三苯胺臂上定位多个BT/CNBT受体，并辅以π-间隔基团和cn -受体基团，无疑是提高OSC应用中给体材料性能的潜在策略。系列3体系具有较强的推拉机制，具有较小的光带隙（1.24 eV）、较强的分子内电荷转移（ICT）和较低的重组能。这些特性有助于提高短路电流密度（JSC） ~ 21.97 mA/cm2，开路电压（VOC） ~ 1.04 V，最小能量损失（0.53 eV）和理论功率转换效率（PCE）高达~15.66%。

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引用次数: 0

Novel cyclic BxCyHz nanorings: First-principles design and electronic tunability of unexplored boron–carbon hybrid nanostructures 新型循环BxCyHz纳米结构：未开发的硼碳杂化纳米结构的第一性原理设计和电子可调性

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-04-01 Epub Date: 2026-01-22 DOI: 10.1016/j.comptc.2026.115688

Ketlen Brenda de O. Rodrigues , Isaac M. Virgilio , David L. Azevedo

This study investigates cyclic boron–carbon–hydrogen (B

_{x}

C

_{y}

H

_{z}

) isomers to assess their structural stability and potential as functional materials. A systematic enumeration satisfying

x + y = 6

yields 64 distinct structures. Electronic, thermodynamic, and optical properties were evaluated using density functional theory (DFT) at the GGA-PBE level, with vibrational analyses refined using the HSE06 hybrid functional. Energetic screening identifies 12 dynamically stable isomers with binding energies between

- 0.34

and

- 0.16

eV/atom and no imaginary frequencies. Band gaps span 0.399–5.169 eV (GGA-PBE) and 0.761–6.238 eV (HSE06), indicating broad electronic tunability. Gibbs free energy calculations using borane (BH

_{3}

) and ethylene (C

_{2}

H

_{4}

) as precursors show favorable formation energetics (

Δ G < 0

) over 298–1000 K. Optical absorption extends from visible to ultraviolet (173–1527 nm). These results demonstrate that compositional variation enables systematic tuning of nanoring properties, supporting their potential for electronic, optical, and biomedical applications.

本研究研究了环硼-碳氢（BxCyHz）异构体，以评估其结构稳定性和作为功能材料的潜力。一个满足x+y=6的系统枚举得到64个不同的结构。利用密度泛函理论（DFT）在GGA-PBE水平上评估了电子、热力学和光学性质，并利用HSE06混合泛函对振动分析进行了改进。高能筛选鉴定出12种动态稳定的异构体，结合能在- 0.34和- 0.16 eV/原子之间，没有虚频率。带隙跨度为0.399 ~ 5.169 eV （GGA-PBE）和0.761 ~ 6.238 eV (HSE06)，具有较宽的电子可调性。以硼烷（BH3）和乙烯（C2H4）为前驱体的吉布斯自由能计算表明，在298-1000 K范围内，形成能量（ΔG<0）是有利的。光吸收范围从可见光到紫外线（173-1527 nm）。这些结果表明，组成的变化可以系统地调整纳米环的性质，支持它们在电子、光学和生物医学上的应用潜力。

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引用次数: 0

The limits of low-spin zinc oxidation states from density functional theory computations: Fluoro‑zinc complexes, [ZnFn]x, where n = 1 through 6 and x = 2+ through 3-, including complexes containing the η1-F2-, 1-η1-F3-, and 1,3-η2-F3-ligands 密度泛函理论计算的低自旋锌氧化态极限：氟锌配合物，[ZnFn]x，其中n = 1至6，x = 2+至3-，包括含有η - 1- f2 -， 1-η - 1- f3 -和1,3-η - 2- f3配体的配合物

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-04-01 Epub Date: 2026-02-06 DOI: 10.1016/j.comptc.2026.115707

Lowen M. Hobbs, Hanna D. Hobbs, Robert W. Zoellner

Density functional theory calculations, at the ωB97X-D/6‐311+G* level of theory, were performed on singlet and doublet spin state fluoro‐zinc complexes [ZnF_n]^x, where n = 1 through 6 and x = 2+ through 3-, to determine the highest positive and lowest negative zinc oxidation states that could be supported in these complexes. All fluoro‐zinc stoichiometries stabilized zinc(III) and zinc(II). The highest positive zinc oxidation state was in the [Zn^VIIF₅]²⁺ square pyramidal and trigonal bipyramidal complexes. Oxidation states as negative as zinc(0) in the bent [Zn⁰F₂]²^‐ and zinc(I) in the [Zn^-IF]²^‐ complexes were also observed. No singlet or doublet fluoro‐‑zinc complexes with charges more positive than 2+, or more negative than 3-, could be optimized. However, complexes which contained the η¹-F₂ ligand were discovered, e.g., the triskelion-shaped [Zn^II(η¹-F₂)₃]²⁺, and complexes containing the η¹⁾-F₃- and 1,3-η²-F₃ ligands were also identified.

在ωB97X-D/6‐311+G*理论水平上，对单重态和双重态氟锌配合物[ZnFn]x进行了密度泛函理论计算，其中n = 1至6，x = 2+至3-，以确定这些配合物中可能支持的最高正态和最低负态锌氧化态。所有氟锌化学计量都稳定了锌（III）和锌（II）。在[ZnVIIF5]2+方锥体和三角双锥体配合物中，锌的正氧化态最高。还观察到弯曲的[Zn0F2]2‐中的锌(0)和[Zn-IF]2‐中的锌(I)的负氧化态。没有单线态或双线态氟锌配合物的正电荷大于2+或负电荷大于3-，可以优化。但也发现了含有η - 1- f2配体的配合物，如三螺旋形的[ZnII(η - 1- f2)3]2+，以及含有η - 1- f3和1,3-η - 2- f3配体的配合物。

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引用次数: 0

A molecular dynamics simulation study on the salt tolerance of saturated cardanol surfactants in a crude oil-water system 饱和腰果酚表面活性剂在原油-水体系中耐盐性的分子动力学模拟研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-04-01 Epub Date: 2026-01-29 DOI: 10.1016/j.comptc.2026.115697

Congying Lu , Zhenyu Yuan , Xinyi Xu , Jianguang Wei , Xiaofeng Zhou , Shamil Sultanov , Limin Li , Huijuan Qian , Qinghe Gao , Wei Ding

In oilfield exploitation, formation water typically contains high concentrations of inorganic salts such as NaCl and CaCl₂, which can diminish the effectiveness of conventional surfactants and potentially render them ineffective. This study focuses on nonionic and anionic–nonionic surfactants derived from cardanol and the synergistic mechanism between inorganic salts and surfactants in reducing oil–water interfacial tension is elucidated. The results indicate that within a specific concentration range (0.2–1.2 mol/L), both NaCl and CaCl₂ can improve the interfacial performance of surfactants and effectively lower interfacial tension. The extent of reduction follows the order: 8EO8POC2SO₃ (sulfonate) > 8EO8POSO₃ (sulfate) > 8EO8POH (nonionic surfactant), CaCl₂ > NaCl. These findings suggest that by selecting appropriate types and concentrations of inorganic salt ions, the interfacial tension of the crude oil–water system can be reduced synergistically.

在油田开发中，地层水中通常含有高浓度的无机盐，如NaCl和CaCl2，这可能会降低传统表面活性剂的有效性，并可能使其失效。研究了腰果酚非离子型和阴离子-非离子型表面活性剂，阐明了无机盐与表面活性剂协同降低油水界面张力的机理。结果表明，在一定浓度范围内（0.2 ~ 1.2 mol/L）， NaCl和CaCl2均能改善表面活性剂的界面性能，有效降低界面张力。还原程度依次为：8EO8POC2SO3（磺酸盐）> 8EO8POSO3（硫酸盐）> 8EO8POH（非离子表面活性剂）；CaCl2 > NaCl。研究结果表明，通过选择合适的无机盐离子类型和浓度，可以协同降低原油-水体系的界面张力。

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引用次数: 0

Nature and energetics of a prototypical ultra-weak type I Cl···Cl interaction: A multi-method computational study 典型超弱I型Cl···Cl相互作用的性质和能量学：多方法计算研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-04-01 Epub Date: 2026-02-09 DOI: 10.1016/j.comptc.2026.115714

Melek Hajji

Halogen···halogen interactions are subtle noncovalent contacts that influence crystal packing and molecular assembly, yet the physical nature and energetics of nondirectional Type I contacts remain an active area of research. Here, a comprehensive multi-method quantum chemical study is reported for a prototypical Type I C–Cl···Cl–C interaction, identified within a crystal-extracted homodimer of dichloro-dimethoxy biphenyl compound. Dispersion-corrected DFT (PW6B95-D3/aug-cc-pVTZ), molecular electrostatic potential (MEP), real-space topology (QTAIM, ELF, IGMH, and IRI), natural bond orbital (NBO) analysis, and symmetry-adapted perturbation theory (SAPT) were employed. The interaction is attractive but ultra-weak (−0.27 kcal mol⁻¹), with London dispersion dominating the stabilization (≈69%). Electrostatic contributions are negligible, and reciprocal LP(Cl) → σ*(CCl) donor–acceptor delocalizations are marginal (total E⁽²⁾ = 0.60 kcal mol⁻¹). MEP analysis proved inadequate for describing this contact, as the σ-hole exhibited clear sensitivity to the chosen isodensity surface and level of theory. Topological analyses provide both visual and quantitative confirmation of a well-defined, closed-shell, van der Waals-type interaction; the associated bond path follows diffuse chlorine lone-pair tails, consistent with the side-on Type I conformation. Beyond this specific case, this work establishes a practical methodological framework for a deeper electronic understanding of similar weak halogen···halogen interactions that complements purely geometric criteria.

卤素···卤素相互作用是影响晶体堆积和分子组装的微妙的非共价接触，但非定向I型接触的物理性质和能量学仍然是一个活跃的研究领域。本文报道了在二氯二甲氧基联苯化合物晶体提取的同型二聚体中发现的典型I型C-Cl···Cl-C相互作用的多方法量子化学研究。采用色散校正DFT （PW6B95-D3/aug-c - pvtz）、分子静电势（MEP）、实空间拓扑（QTAIM、ELF、IGMH和IRI）、自然键轨道（NBO）分析和对称自适应微扰理论（SAPT）。相互作用是有吸引力的，但非常弱（- 0.27 kcal mol - 1），伦敦色散主导稳定（≈69%）。静电贡献可以忽略不计，且LP（Cl）→σ*(CCl)供体-受体离域的倒数是边际的（总E(2) = 0.60 kcal mol−1）。MEP分析不足以描述这种接触，因为σ-空穴对所选择的等密度表面和理论水平表现出明显的敏感性。拓扑分析提供了一个明确定义的、闭壳的、范德瓦尔斯型相互作用的视觉和定量确认；相关的键路径遵循弥漫氯孤对尾部，与侧对I型构象一致。除了这个特定的案例，这项工作建立了一个实用的方法框架，用于更深入地理解类似的弱卤素···卤素相互作用，补充纯粹的几何标准。

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引用次数: 0

Electronic and structural modulation of the B- and N-doped phenine nanotubes 掺杂B和n的苯纳米管的电子和结构调制

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-04-01 Epub Date: 2026-02-02 DOI: 10.1016/j.comptc.2026.115698

Aercio F.F. De F. Pereira, Puspitapallab Chaudhuri, Angsula Ghosh

Phenine nanotubes (pNTs), constructed from benzene rings, form a new class of porous carbon-based nanostructures with highly tunable structural and electronic features. The influence of boron–nitrogen (BN) substitution and hydrogen depletion on pNT geometry and electronic behavior is investigated across ten configurations, including pristine, single-element (B or N), and mixed B–N substitutions arranged symmetrically and asymmetrically. Among the doped systems, the hydrogenated nitrogen-substituted pNT is the most stable. BN incorporation preserves the tubular framework while subtly reshaping pore size and morphology. Both doping and hydrogenation allow controlled modulation of pore geometry. Hydrogen removal in pristine pNTs induces a semiconductor-to-metal transition, whereas hydrogen-depleted single-element substitutions lead to significant band-gap widening. In contrast, hydrogenated mixed B–N systems show strong gap suppression, often eliminating the bandgap entirely. The combined tunability in porosity and electronic response positions BN-substituted pNTs as promising candidates for future nanoelectronic and sensing technologies.

苯胺纳米管（Phenine nanotubes, pNTs）是由苯环构成的一种新型多孔碳基纳米结构，具有高度可调的结构和电子特性。研究了硼氮（BN）取代和氢耗尽对pNT几何形状和电子行为的影响，包括原始、单元素（B或N）和混合B - N取代的对称和不对称排列。在这些掺杂体系中，氢化氮取代的pNT是最稳定的。BN掺入保留管状框架，同时巧妙地重塑孔隙大小和形态。掺杂和氢化都允许对孔隙几何形状进行控制调制。原始pnt中的氢去除诱导半导体到金属的转变，而氢耗尽的单元素取代导致显着的带隙扩大。相反，氢化混合B-N体系表现出很强的隙抑制作用，经常完全消除带隙。多孔性和电子响应的组合可调性使bn取代的pnt成为未来纳米电子和传感技术的有希望的候选者。

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引用次数: 0

Regulatory mechanism of inorganic fillers on Zn2+ transport in PEO–Zn(TFSI)2 electrolyte within all-solid-state zinc-ion batteries 无机填料对全固态锌离子电池PEO-Zn (TFSI)2电解质中Zn2+输运的调控机制

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-04-01 Epub Date: 2026-01-22 DOI: 10.1016/j.comptc.2026.115684

Yong Wang , Yufeng Yang , Wolong Li , Yongcun Li

All-solid-state zinc-ion batteries (ZIBs) require electrolytes that deliver both high ionic conductivity and high safety; however, the Zn²⁺ migration mechanisms in composite solid electrolytes remain unclear. In this work, we combine molecular dynamics (MD) simulations with density functional theory (DFT) calculations to study Zn²⁺ transport in a PEO-Zn(TFSI)₂ matrix and in its composites containing SiO₂, ZnPS₃, and a ZnPS₃/MoS₂ hybrid filler, with a particular focus on bulk plasticization and interfacial transport pathways. The results show that SiO₂ delivers a modest low-temperature gain primarily by reducing crystallinity. ZnPS₃ weakens ZnO coordination while forming a Zn-P-dominated interfacial network and a space-charge layer, thereby enhancing diffusion across a broad temperature window. Surface states on ZnPS₃(001) induce electron accumulation that electrostatically drives Zn²⁺ enrichment at the interface. The introduction of MoS₂ further enhances the interfacial dipole and geometric connectivity, resulting in a relative increase of approximately 1.5–2.4 times in the MSD slope at medium-to-high temperatures compared to PEO + ZnPS₃. MD and DFT calculations demonstrate that the synergistic effect of chemically driven coordination exchange and geometrically guided epitaxial channels substantially enhances zinc ion mobility within the electrolyte.

全固态锌离子电池（zib）需要提供高离子电导率和高安全性的电解质；然而，Zn2+在复合固体电解质中的迁移机制尚不清楚。在这项工作中，我们将分子动力学（MD）模拟与密度泛函理论（DFT）计算相结合，研究了Zn2+在PEO-Zn(TFSI)2基体及其含有SiO2、ZnPS3和ZnPS3/MoS2杂化填料的复合材料中的输运，特别关注了体塑化和界面输运途径。结果表明，SiO2主要通过降低结晶度来获得适度的低温增益。ZnPS3在形成zn - p主导的界面网络和空间电荷层的同时减弱了ZnO的配位，从而增强了在宽温度窗内的扩散。ZnPS3（001）表面态诱导电子积累，静电驱动界面处的Zn2+富集。MoS2的引入进一步增强了界面偶极子和几何连通性，与PEO + ZnPS3相比，在中高温下MSD斜率相对增加了约1.5-2.4倍。MD和DFT计算表明，化学驱动的配位交换和几何引导的外延通道的协同效应大大提高了锌离子在电解质中的迁移率。

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引用次数: 0

Quantum information geometry meets DMRG: Uhlmann gauge improvements in computational methods 量子信息几何满足DMRG：乌尔曼规范在计算方法上的改进

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-04-01 Epub Date: 2025-12-11 DOI: 10.1016/j.comptc.2025.115623

Andrei T. Patrascu

Standard DMRG truncation based purely on singular values can induce unphysical discontinuities along path parameters such as sweeps or molecular geometries, particularly near avoided crossings and quasi-degeneracies. We formulate a dynamical Uhlmann gauge on reduced density matrices along such paths, and use the induced covariant derivatives and curvatures to define continuity-aware truncation scores that are both gauge invariant and purification independent. On a gapped spin-chain benchmark, the resulting Uhlmann-guided DMRG preserves the variational optimum and non-parallelity error at fixed bond dimension

M

while producing much smoother entanglement spectra and overlaps. As a simple chemistry-relevant proof of principle, we also analyse a small-CAS LiF potential-energy scan at the reduced-density level and show that the Uhlmann-based selection strongly suppresses pathological Schmidt-subspace rotations along the bond coordinate. The method therefore provides a principled continuity prior that complements conventional SVD-based truncation and improves path smoothness of gauge-sensitive quantities without altering physical observables.

纯粹基于奇异值的标准DMRG截断可能导致沿路径参数（如扫描或分子几何）的非物理不连续，特别是在避免交叉和准简并附近。我们在这些路径上的简化密度矩阵上建立了一个动态Uhlmann规范，并使用诱导协变导数和曲率来定义既规范不变又净化无关的连续性感知截断分数。在间隙自旋链基准上，得到的Uhlmann-guided DMRG保留了固定键维M下的变分最优和非平行误差，同时产生了更平滑的纠缠谱和重叠。作为一个简单的化学相关原理证明，我们还分析了低密度水平的小cas liff势能扫描，并表明基于uhlmann的选择强烈抑制了沿键坐标的病态施密特子空间旋转。因此，该方法提供了一个原则性的连续性先验，补充了传统的基于svd的截断，并在不改变物理观测值的情况下提高了测量敏感量的路径平滑度。

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引用次数: 0

Benchmarking DFT methods for calculating reorganization energies in charge transport properties of organic semiconductors: A case study of nitro-aniline molecules 计算有机半导体电荷输运性质重组能的基准DFT方法：以硝基苯胺分子为例

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-04-01 Epub Date: 2026-01-15 DOI: 10.1016/j.comptc.2026.115664

Emmanuel Madakobiyé , Marius Bouba Ousmanou , Fridolin Tchangnwa Nya , Geh Wilson Ejuh , Alhadji Malloum , Jeanet Conradie

Due to its occurrence in the exponential term of the Marcus–Hush hopping rate equation, precise prediction of the internal reorganization energy (

λ_{int}

) is essential for reliable modeling of charge carrier mobility (

μ

) in organic semiconductors. In this work, we calculated both hole (

λ_{h}

) and electron (

λ_{e}

) reorganization energies across three nitro-aniline push–pull isomers (ONA, MNA, PNA) by methodically benchmarking eighteen Density Functional Theory (DFT) functionals against the gold standard CCSD(T)/6-311++G(d,p) reference data. To demonstrate quantitative agreement, performance was evaluated using standard metrics (MAD, RMSD) supplemented by correlation coefficients (

R^{2}

). According to the analysis, double hybrid functionals: rev-DSD-PBEP86-D3 and rev-DSD-PBEP86-D3BJ functionals perform better with a Mean Absolute Deviation (MADs) of roughly 0.23 meV and a nearly perfect correlation with the CCSD(T) trend (

R^{2} > 0.95

). On the other hand, hybrid functionals like M06 and CAM-B3LYP demonstrated notable discrepancies for specific isomers, underscoring their restricted suitability for precise

λ

prediction. We recommend the rev-DSD-PBEP86-D3BJ methods as robust, less computationally demanding alternatives to CCSD(T) for these systems. This foundational work provides reliable DFT methods essential for subsequent accurate calculations of electronic coupling and charge transport mobilities, enabling future quantitative comparison with experimental data for nitro-aniline-like materials.

由于内部重组能（λint）出现在Marcus-Hush跳变速率方程的指数项中，因此对有机半导体中载流子迁移率（μ）的可靠建模至关重要。在这项工作中，我们计算了三个硝基苯胺推挽异构体（ONA， MNA， PNA）的空穴（λh）和电子（λe）重组能，方法是系统地对照金标准CCSD(T)/6-311++G（d,p）参考数据对18个密度泛函数（DFT）进行基准测试。为了证明定量一致性，使用标准指标（MAD， RMSD）辅以相关系数（R2）来评估绩效。根据分析，双混合泛函：rev-DSD-PBEP86-D3和rev-DSD-PBEP86-D3BJ泛函表现较好，平均绝对偏差（MADs）约为0.23 meV，与CCSD(T)趋势的相关性接近完美（R2>0.95）。另一方面，像M06和CAM-B3LYP这样的杂化官能团在特定的异构体上表现出显著的差异，强调了它们对精确λ预测的局限性。我们推荐rev-DSD-PBEP86-D3BJ方法作为这些系统的CCSD(T)的鲁棒性，计算要求更低的替代品。这项基础工作为后续电子耦合和电荷输运迁移率的精确计算提供了可靠的DFT方法，使未来与硝基苯胺类材料的实验数据进行定量比较成为可能。

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引用次数: 0

Inverse isotope effect in Pd: First-principles insights into hydrogen isotope diffusion, dissolution, and permeation Pd中的逆同位素效应：氢同位素扩散、溶解和渗透的第一性原理

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-04-01 Epub Date: 2026-02-03 DOI: 10.1016/j.comptc.2026.115710

Ting Zhang, Jun Tang, Xiaoqiu Ye

Utilizing first-principles calculations within the framework of density functional theory, this work systematically investigates the dissolution, diffusion, and permeation of hydrogen (H), deuterium (D), and tritium (T) in palladium. A key finding is the prediction of a distinct inverse isotope effect in diffusion at low temperatures (T < ∼800 K), where the calculated diffusion coefficients increase with the mass of the isotope, contrary to classical expectations. This anomaly is quantitatively traced to the reduction of the effective diffusion barrier with increasing isotope mass due to zero-point energy contributions. In contrast, dissolution and permeation maintain the normal isotope trend. By integrating microscopic calculations with a macroscopic Fick transport model, this study offers crucial insights into the quantum-mechanical origins of isotope effects in metals and guides the design of Pd-based membranes for isotope separation applications.

利用密度泛函理论框架内的第一性原理计算，本工作系统地研究了氢(H)、氘(D)和氚(T)在钯中的溶解、扩散和渗透。一个关键的发现是预测了低温（T < ~ 800 K）扩散中明显的逆同位素效应，其中计算的扩散系数随着同位素质量的增加而增加，与经典预期相反。这种异常可以定量地追溯到有效扩散势垒随着同位素质量的增加而减少，这是由于零点能量的贡献。溶蚀和渗透则保持正常同位素趋势。通过将微观计算与宏观菲克输运模型相结合，本研究为金属中同位素效应的量子力学起源提供了重要见解，并指导了用于同位素分离应用的钯基膜的设计。

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