Computational and Theoretical Chemistry最新文献

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Comparison of the carboxylic acid and ester anchoring groups in pyrene-based sensitizers in DSSC: A computational investigation DSSC中芘基敏化剂中羧酸和酯锚定基的比较：计算研究

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.2025.115648

Vandana Kumari Shukla, Nagaiyan Sekar

Sixteen donor-pi-acceptor (D-π-A) type sensitizers, which consist of pyrene as the donor unit coupled to various spacers and acceptor units, are investigated using density functional theory (DFT) and time dependent DFT (TD-DFT) techniques. The effects of substituting an ester group for carboxylic acid as acceptor on the system are investigated. The addition of ester causes the destabilization of the lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) of the sensitizers. In carboxylic acid acceptor-based sensitizers, the frontier molecular orbital (FMO) also illustrates an efficient intramolecular charge transfer (ICT) from the donor unit to the acceptor unit. Additionally, it is observed that ester acceptor-based sensitizers have higher computed open circuit voltage (Voc) values. According to the TD-DFT investigation, the acid acceptor-based sensitizers exhibit red-shifted vertical excitation. A positive solvatochromism is seen for all the sensitizers in TD-DFT calculations. The excited state dipole moment of acid acceptor-based sensitizer, calculated using Suppan's equation, is found to be more than the ester acceptor-based sensitizers. For the furan spacer based sensitizers with double bond between donor and spacer the following result is obtained- dipole moment moment in Debye (8.2: acid and 6.4: ester), HOMO-LUMO energy gap in eV (2.5: acid and 2.6: ester), electrophilicity index in eV (6.8: acid and 6.3: ester), hyperhardness in eV (1.7: acid and 1.8: ester) and absorption maxima in THF in nm (583: acid and 572: ester) in B3LYP functional.

采用密度泛函理论（DFT）和时间依赖DFT （TD-DFT）技术研究了以芘为供体单元偶联不同间隔和受体单元的16种给体-π-受体（D-π-A）型增敏剂。研究了用酯基取代羧酸作为受体对体系的影响。酯的加入导致敏化剂的最低未占据分子轨道（LUMO）和最高已占据分子轨道（HOMO）的失稳。在羧酸受体敏化剂中，前沿分子轨道（FMO）也表明了分子内电荷从供体单元到受体单元的有效转移（ICT）。此外，还观察到基于酯受体的敏化剂具有更高的开路电压（Voc）值。根据TD-DFT研究，酸受体基敏化剂表现出垂直红移激发。在TD-DFT计算中，所有的敏化剂都有正的溶剂致色性。用Suppan方程计算了酸受体敏化剂的激发态偶极矩，发现酸受体敏化剂的激发态偶极矩大于酯受体敏化剂。对于具有双键给体和间隔剂的呋喃基敏化剂，得到了以下结果：Debye偶极矩矩（8.2：酸和6.4：酯）、eV的HOMO-LUMO能隙（2.5：酸和2.6：酯）、eV的亲电性指数（6.8：酸和6.3：酯）、eV的超硬度（1.7：酸和1.8：酯）和B3LYP官能团中THF在nm内的吸收最大值（583：酸和572：酯）。

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引用次数: 0

Adsorption of NH3 on TiN and Si3N4 surfaces: A theoretical study NH3在TiN和Si3N4表面吸附的理论研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-12-15 DOI: 10.1016/j.comptc.2025.115636

Jae Min Jang, Sujin Kwon, Ju Hyeon Jung, Bonggeun Shong

The adsorption and desorption reactions of NH₃ on two technologically important materials, TiN and Si₃N₄, are compared using a computational chemistry approach based on density functional theory (DFT) calculations. We confirm that TiN remains essentially pristine without NH₃-related adsorbates for a wide range of temperatures, whereas the Si₃N₄ surface is mostly functionalized by the NH_3-derived groups. This study provides theoretical insights for predicting surface chemical properties and NH₃ adsorption behavior across different nitride substrates.

采用基于密度泛函理论（DFT）计算的计算化学方法，比较了NH3在两种技术上重要的材料TiN和Si3N4上的吸附和解吸反应。我们证实，在没有nh3相关吸附的情况下，TiN在很宽的温度范围内基本上保持原始状态，而Si3N4表面主要被nh3衍生基团功能化。该研究为预测不同氮化物基质的表面化学性质和NH3吸附行为提供了理论见解。

引用次数: 0

DFT study on hydrogen adsorption behaviour of armchair and sawtooth structure cup-stacked carbon nanotube walls with B-substituted and Pt-decorated b取代和pt修饰的扶手状和锯齿状杯状碳纳米管壁吸氢行为的DFT研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-11-09 DOI: 10.1016/j.comptc.2025.115587

Zhitong Xu, Tingbo Liao, Yinquan Sui, Huanpeng Liu

The hydrogen storage properties of Cup-Stacked Carbon Nanotubes (CSCNTs), which are sawtooth-shaped and armchair-shaped structures with B atom substitutions at different spacings and loaded with Pt atoms, were investigated using density functional theory. The results show that when the spacing of the B atoms is small, the Pt atoms still tend to form clusters due to the interatomic gravitational force between the Pt atoms, which is larger than the attraction between the Pt atoms and the C/B atoms. For the sawtooth-shaped structure, B-atom spacing greater than 7.3 Å, with stabilised isolated Pt atoms loading, and the maximum hydrogen adsorption capacity. In addition, electrostatic potentials, electron localisation function and Weak interaction analysis investigated the mechanism of Pt atom loading. The HOMO-LUMO orbitals and energy gap of the two structures are also compared, and it is found that the armchair-shaped structure has a larger energy gap and a more stable electronic structure.

利用密度泛函理论研究了杯状碳纳米管（CSCNTs）的储氢性能。CSCNTs是一种具有不同间距B原子取代的锯齿形和扶手椅形结构，并装载Pt原子。结果表明：当B原子间距较小时，由于Pt原子之间的原子间引力大于Pt原子与C/B原子之间的引力，Pt原子仍倾向于形成团簇；对于锯齿形结构，b原子间距大于7.3 Å，具有稳定的孤立Pt原子负载，并且具有最大的氢吸附能力。此外，通过静电势、电子定位函数和弱相互作用分析研究了铂原子的加载机理。对比了两种结构的HOMO-LUMO轨道和能隙，发现扶手椅型结构具有更大的能隙和更稳定的电子结构。

引用次数: 0

First-principles study of hydrogen adsorption energy and preferred storage site in MgNi alloys MgNi合金中氢吸附能和优选储存位置的第一性原理研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-11-21 DOI: 10.1016/j.comptc.2025.115600

Huan Wang , Changli Shi , Zihe Cao , Xiaolu Chen , Qiguo Zhang , Gangjun Gong , Qiang Lu , Xinhua Yuan , Bing Zhang

MgNi alloys are promising candidates for hydrogen storage materials due to their significant potential in sustainable energy technologies. However, accurately predicting hydrogen adsorption energies and identifying optimal storage sites remain critical challenges. This study evaluates the performance of two DFT exchange-correlation functionals (PBE and SCAN) and assesses the effects of Hubbard U correction and van der Waals interaction on MgNi alloys. The results demonstrate that SCAN significantly outperforms PBE in predicting hydrogen adsorption energies due to its consideration of orbital kinetic energy density. Variations in the contributions of Hubbard U and vdW interactions are observed across different storage sites. Based on parameters such as volume change rate, adsorption energy, NiH bond length and ICOHP, the H2 site is identified as the preferred storage site. These findings highlight the importance of theoretical parameters in optimizing MgNi alloy systems, providing insights for advancing efficient hydrogen storage materials and supporting sustainable energy technologies.

MgNi合金因其在可持续能源技术中的巨大潜力而成为储氢材料的有希望的候选者。然而，准确预测氢吸附能和确定最佳储存地点仍然是关键的挑战。本研究评估了两种DFT交换相关泛函（PBE和SCAN）的性能，并评估了Hubbard U校正和van der Waals相互作用对MgNi合金的影响。结果表明，由于考虑了轨道动能密度，SCAN在预测氢吸附能方面明显优于PBE。在不同的储存地点观察到Hubbard U和vdW相互作用的贡献的变化。基于体积变化率、吸附能、NiH键长、ICOHP等参数，确定H2位点为首选存储位点。这些发现突出了理论参数在优化MgNi合金系统中的重要性，为推进高效储氢材料和支持可持续能源技术提供了见解。

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引用次数: 0

Inerting mechanism of CO2 and N2 on the oxidative reaction of active groups in coal CO2和N2对煤中活性基团氧化反应的惰化机理

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-11-28 DOI: 10.1016/j.comptc.2025.115618

Qihui Bai , Xihua Zhou , Gang Bai , Fei Gao

To investigate the influence of CO₂ and N₂ on the oxidative reaction of coal, a combined method of molecular dynamics and quantum chemical calculation was applied to infer the reaction paths of side chain and bridge bond active groups in coal with ·OH and O₂ during low-temperature oxidation. The activation stages of chemical reactions involving active groups were divided. The inerting mechanism of CO₂ and N₂ on the oxidative reaction of active groups in coal was revealed from the physical adsorption, chemical adsorption, and chemical reaction stages of coal oxidation. The results showed that before CO₂ and N₂ interacted with the active groups, CO₂ effectively hindered the physical and chemical adsorption processes of the active groups on O₂ by virtue of its strongly competitive adsorption characteristics, while having no significant effect on ·OH. In contrast, N₂ showed no substantial interference with either the physical or chemical adsorption stages of the active groups. After van der Waals interactions with the active groups, both CO₂ and N₂ could inert the chemical adsorption of the active groups with ·OH and O₂, and the inerting effect of CO₂ on the chemical adsorption of the active groups was approximately more than twice that of N₂. The chemical reactions of active groups could be subdivided into three activation stages. Stage I was the activation of cyclic chain reactions between active groups and free radicals under room-temperature conditions. Stages II and III were the activation of composite reactions between active groups and O₂ at 30–70 °C and 70–200 °C, respectively. The influence of CO₂ on the activation stages I, II, and III showed a change rule of “inhibition-promotion-inhibition,” while N₂ had a significant promotional effect on the three activation stages. The inerting effect of CO₂ on the chemical reactions of active groups consistently outperformed that of N₂ throughout the entire low-temperature oxidation process. The study results will offer an important basis for refining the fundamental theory of fire prevention and control technology using inert gases in coal mines.

为了研究CO2和N2对煤氧化反应的影响，采用分子动力学和量子化学计算相结合的方法，推导了煤中侧链和桥键活性基团与·OH和O2在低温氧化过程中的反应路径。对涉及活性基团的化学反应的激活阶段进行了划分。从煤氧化的物理吸附、化学吸附和化学反应阶段揭示了CO2和N2对煤中活性基团氧化反应的惰化机理。结果表明，在CO2和N2与活性基团相互作用前，CO2凭借其强烈的竞争吸附特性，有效地阻碍了活性基团对O2的物理和化学吸附过程，而对·OH的影响不显著。相比之下，N2对活性基团的物理或化学吸附阶段都没有实质性的干扰。与活性基团发生范德华作用后，CO2和N2均能惰性化活性基团与·OH和O2的化学吸附，且CO2对活性基团化学吸附的惰性效应约为N2的2倍以上。活性基团的化学反应可分为三个活化阶段。第一阶段为室温条件下活性基团与自由基之间的环链反应活化。阶段II和阶段III分别为活性基团与O2在30-70℃和70-200℃下的复合反应活化。CO2对I、II、III活化阶段的影响表现为“抑制-促进-抑制”的变化规律，而N2对三个活化阶段都有显著的促进作用。在整个低温氧化过程中，CO2对活性基团化学反应的惰化作用始终优于N2。研究结果将为完善煤矿惰性气体防火技术的基础理论提供重要依据。

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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 : 2026-02-01 Epub 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

Structural ensemble modeling of FRET and electron transfer rates in surface-bound molecular bilayers 表面结合分子双层中FRET和电子传递速率的结构系综模型

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-12-14 DOI: 10.1016/j.comptc.2025.115633

Jackson Nolder, Kenneth Hanson

The assembly of multiple chromophores, catalysts, and redox active molecules on inorganic surfaces is of interest for applications including solar energy conversion, catalysis, and sensing. These applications typically rely on intermolecular electron and energy transfer which, in addition to energetics, are dictated by the structure of the assembly. Here we introduce a software package with a user-friendly graphical user interface (GUI) that calculates interlayer FRET and electron transfer rates for all reasonable structures of surface-bound molecular bilayers. The graphical output illustrates the energy and electron transfer rates with respect to measurable structural parameters, as well as a vector depiction of the possible bilayer structure with the fastest energy and electron transfer rates. We include a few use cases that demonstrate the effects of varying the metal linking ion and solvent on energy and electron transfer rates in metal ion linked bilayers. While our focus is primarily on metal ion linked systems, we show how, with minor input modification, this software can be applied to covalently linked dyads or other bilayer assemblies on surfaces.

多种发色团、催化剂和氧化还原活性分子在无机表面的组装是太阳能转换、催化和传感等应用的兴趣所在。这些应用通常依赖于分子间的电子和能量转移，除了能量学之外，这些转移是由组装的结构决定的。在这里，我们介绍了一个软件包与用户友好的图形用户界面（GUI）计算层间FRET和电子转移率的所有合理结构的表面结合分子双层。图形输出说明了相对于可测量的结构参数的能量和电子转移率，以及具有最快能量和电子转移率的可能的双层结构的矢量描述。我们包括几个用例，展示了不同的金属连接离子和溶剂对金属离子连接双层中能量和电子转移速率的影响。虽然我们的重点主要放在金属离子连接系统上，但我们展示了如何通过微小的输入修改，将该软件应用于共价连接的二联体或表面上的其他双层组件。

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引用次数: 0

Adsorption and sensing of vildagliptin on coinage metal nanoclusters: DFT, MD and spectroscopic insights 维格列汀在金属纳米团簇上的吸附和传感：DFT， MD和光谱分析

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-12-17 DOI: 10.1016/j.comptc.2025.115640

Jamelah S. Al-Otaibi , Y. Sheena Mary , Vasudevan Baiju , K. Jalaja , Maria Cristina Gamberini

This work presents a focused computational investigation of how the anti-diabetic drug vildagliptin (VGP) interacts with small coinage-metal clusters (Ag₃, Au₃ and Cu₃) and the implications of those interactions for sensing and nanoscale delivery. Adsorption is exothermic for all metal-drug combinations, with adsorption energies in vacuum roughly spanning −15.7 to −33.5 kcal mol⁻¹ (Ag₃ ≈ −15.7 to −21.4; Au₃ ≈ −21.3 to −33.5; Cu₃ ≈ −25.3 to −31.5), and stronger binding in water (largest for the NH-site complexes, e.g., Au₃-VGP3 ≈ −52.7 kcal mol⁻¹). The energy-gap decreases (∆Eg) and DOS changes indicate increased conductivity upon adsorption – a desirable feature for electrochemical sensing – while computed Raman/IR shifts and SERS-relevant enhancements support spectroscopic detectability. MD and docking show that VGP and Au₃-complexes tend to preserve protein structural stability, whereas Ag₃ and especially Cu₃ complexes can induce greater conformational perturbation.

这项工作提出了抗糖尿病药物维格列汀（VGP）如何与小铸币金属簇（Ag3， Au3和Cu3）相互作用以及这些相互作用对传感和纳米级递送的影响的重点计算研究。所有金属-药物组合的吸附都是放热的，真空中的吸附能大致为−15.7至−33.5 kcal mol−1 (Ag3≈−15.7至−21.4;Au3≈−21.3至−33.5;Cu3≈−25.3至−31.5)，在水中的结合更强（nh位配合物最大，例如Au3- vgp3≈−52.7 kcal mol−1）。能隙减小（∆Eg）和DOS变化表明吸附时电导率增加-这是电化学传感的理想特征-而计算拉曼/红外位移和sers相关增强支持光谱可探测性。MD和对接表明，VGP和au3配合物倾向于保持蛋白质结构的稳定性，而Ag3，特别是Cu3配合物会引起更大的构象扰动。

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引用次数: 0

Bridge inter-level coupling strength dependence of the electron transfer in multiple peptide-bridges mediated donor-acceptor complexes via the Superexchange mechanism 通过超交换机制，多肽桥介导的给受体复合物中电子转移的桥间耦合强度依赖性

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.2025.115638

Xiumei Chu , Wenjuan Zhu

The bridge inter-level coupling strength dependence of the electron transfer in multiple peptide-bridges mediated donor-acceptor complexes via the superexchange mechanism is examined through the quasi-adiabatic propagator path integral algorithm in this work. It is proven that the superexchange mechanism of electron transfer in the these complexes could be maintained by adjusting the inter-bridge coupling strength when the bridge-site number increased from two to six. Especially, keeping the same bridge energy as DB₁A and DB₂A, when the bridge inter-level coupling in DB₃A or DB₄A complexes is enhanced, the energy diffusion inside them is only affected, as a result of which the dephasing rates show a tendency to decrease gradually and tends to level off, meanwhile the relaxation rates climb up gradually and attain a maximum value. Therefore, in multi-peptide-bridge complexes, it could regulate the inter-bridge coupling in DB_nA system to maintain the superexchange mechanism and accelerate the electron transfer rates.

本文通过准绝热传播子路径积分算法研究了多肽桥介导的给受体复合物中电子传递的桥间耦合强度依赖于超交换机制。结果表明，当桥位数从2个增加到6个时，通过调节桥间耦合强度可以维持配合物中电子转移的超交换机制。特别是在保持与DB1A和DB2A相同的桥能级的情况下，当DB3A或DB4A配合物的桥能级间耦合增强时，只会影响其内部的能量扩散，因此消相速率呈现逐渐降低趋于平稳的趋势，而弛豫速率则逐渐攀升并达到最大值。因此，在多肽桥配合物中，它可以调节DBnA体系中的桥间耦合，维持超交换机制，加快电子传递速率。

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引用次数: 0

Electronic spectra simulations of selected d6 NHC-metal complexes for photosensors applications 用于光传感器的d6 nhc -金属配合物的电子光谱模拟

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-02-01 Epub Date: 2025-11-26 DOI: 10.1016/j.comptc.2025.115607

Amanda D. Torres, Ricardo R. Oliveira, Alexandre B. Rocha

An important class of ligands studied recently is N-heterocyclic carbenes (NHCs) with potential application as a photosensor for solar cells. In this work we investigate organometallic complexes based on

(CNC = 2,6-bis[3-isopropylimidazol-2-ylidene]pyridine). We selected

d^{6}

metals, namely Co(III), Mn(I) and Cr(0), with the same ligands and applied CASSCF/NEVPT2 and TDDFT methods. It is shown that TDDFT is a suitable method, agreeing well with CASSCF/NEVPT2. The potential for use as a photosensor follows the order: Mn(I), Cr(0), Fe(II), and Co(III). The

is shown to the best candidates for photosensitizer due to the higher absorption band in the region of maximum solar radiation and most effective intersystem crossing (ISC) to the triplet state, followed very closely by

近年来研究的一类重要的配体是n -杂环碳烯（NHCs），具有作为太阳能电池光传感器的潜在应用。在这项工作中，我们研究了基于（CNC = 2,6-二[3-异丙咪唑-2-酰基]吡啶）的有机金属配合物。我们选择了6种金属，即Co(III), Mn(I)和Cr(0)，具有相同的配体，并应用CASSCF/NEVPT2和TDDFT方法。结果表明，TDDFT是一种合适的方法，与CASSCF/NEVPT2方法吻合较好。作为光敏元件的潜力依次为：Mn(I)、Cr(0)、Fe（II）和Co（III）。由于在最大太阳辐射区域具有较高的吸收带和最有效的系统间交叉（ISC）到三重态，因此被证明是光敏剂的最佳候选者。

引用次数: 0

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