Computational and Theoretical Chemistry最新文献

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A comparative computational insight into the interaction of green house gases with naturally ocurring amino acid 温室气体与自然产生的氨基酸相互作用的比较计算洞察力

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-10-26 DOI: 10.1016/j.comptc.2025.115551

Elema Khatun , Bhabesh Chandra Deka , Pubalee Sarmah , Pradip Kr Bhattacharya

Amino acids serve as an efficient and environment friendly adsorbent. In the present work, feasibility and extent of interaction of greenhouse gases CO, CO₂, NO₂ and SO₂ with amino acids alanine, arginine, aspartic acid, glutamic acid, lysine and serine have been studied by using density functional theory (DFT). Interaction energy calculations and Natural Bond Orbital (NBO) analysis suggest the feasibility of such complexation. Among the gases considered, SO₂ exhibits the strongest interaction with all the amino acids studied, within the range − 9.95 to −10.17 kcalmol⁻¹. Although increasing solvent polarity leads to a reduction in the interaction energy, the complexes remain stable across all the solvent dielectrics. Stability of complexes has further been analyzed through thermochemical parameters and reactivity descriptors. Effective interaction leads to changes in the energy of molecular orbitals and subsequent alterations in global reactivity descriptors. In addition to a detailed study of the effect of different functional and basis sets on interaction energy, MP2 calculation has also been performed for better accuracy of results. The present study predicts that biomolecules such as amino acids may be considered as a potential scavenger of greenhouse gases in near future.

氨基酸是一种高效、环保的吸附剂。本文利用密度泛函理论（DFT）研究了温室气体CO、CO2、NO2和SO2与氨基酸丙氨酸、精氨酸、天冬氨酸、谷氨酸、赖氨酸和丝氨酸相互作用的可行性和程度。相互作用能计算和自然键轨道（NBO）分析表明这种配合的可行性。在所考虑的气体中，二氧化硫与所研究的所有氨基酸的相互作用最强，在−9.95至−10.17 kcalmol−1范围内。虽然溶剂极性增加导致相互作用能降低，但配合物在所有溶剂介质中都保持稳定。通过热化学参数和反应性描述符进一步分析了配合物的稳定性。有效的相互作用导致分子轨道能量的变化和随后的整体反应性描述符的变化。除了详细研究了不同功能集和基集对相互作用能的影响外，为了提高结果的准确性，还进行了MP2计算。本研究预测，在不久的将来，氨基酸等生物分子可能被认为是一种潜在的温室气体清除剂。

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引用次数: 0

A study on bond length compression effect of lone pair electrons in polycyclic heterocyclic quinones 多环杂环醌中孤对电子键长压缩效应的研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-10-26 DOI: 10.1016/j.comptc.2025.115566

Chun Lei , Jiefeng Lin , Jiaohong Xu , Yongfan Zhang , Yaofeng Yuan , Bin Wang , Wenfeng Wang , Yongguo Liu

Four polycyclic heterocyclic quinones derivatives are synthesized. The calculated structures of compounds 3 and 8 indicate that the bond lengths of the CH bonds are compressed by N (or O) atom and OCH₃ group nearby, which are called as compression effect of lone pair electrons (CELP) and of covalent group (CECG), respectively. They both belong to improper H-Bonding and can be distinguished by δ values of HNMR. In predominant conformation of compound 3, CELP and CECG act on the same CH bond, which fits with the crystal structure. NBO analyses show that the compression of CH bond is caused by the increase of s orbital components of C atoms. Finally, eight compounds were tested for anticancer activities and abilities to generate ROS, and the result shows that they are positively correlated. The comparison of crystal structures shows that the abilities to generate ROS are related to spatial conformations.

合成了4个多环杂环醌衍生物。化合物3和8的计算结构表明，CH键的键长被附近的N（或O）原子和OCH3基团压缩，分别称为孤对电子（CELP）和共价基（CECG）的压缩效应。它们都属于非正常氢键，可以通过HNMR的δ值来区分。在化合物3的优势构象中，CELP和CECG作用在同一个CH键上，这与晶体结构吻合。NBO分析表明，CH键的压缩是由C原子s轨道组分的增加引起的。最后，对8种化合物的抗癌活性和生成ROS的能力进行了测试，结果表明它们之间呈正相关。晶体结构的比较表明，生成活性氧的能力与空间构象有关。

引用次数: 0

Substitution dopant Al regulates the N penetration efficiency of nitriding Ti surfaces 取代掺杂剂Al调节氮化Ti表面的N渗透效率

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-10-25 DOI: 10.1016/j.comptc.2025.115565

Haoyu Wang , Yudong Fu , Chong Li , Chengfeng Li , Weihong Gao

Penetration is the rate-determining step in surface nitridation reactions, yet the effects of dopants on these chemical reaction processes are not well characterized. Herein, we investigate the mechanism by which Al, as an active species, facilitates N penetration through density functional theory (DFT) calculations. The results show that N is stably adsorbed on FCC and HCP sites, and this trend remains after Al doping. In most cases, the N adsorption capacity on the surface and subsurface is weakened by Al. Adsorption energy analyses indicate that Al enhances both desorption and adsorption efficiency, thereby promoting N penetration from a thermodynamic perspective. The calculated penetration path results further support this trend. This study provides a fundamental insight into the catalytic penetration mechanism for Al dopants during the nitriding of Ti surfaces.

渗透是表面氮化反应的速率决定步骤，但掺杂剂对这些化学反应过程的影响尚未得到很好的表征。在此，我们通过密度泛函理论（DFT）计算研究了Al作为活性物质促进N渗透的机制。结果表明，氮在FCC和HCP位点上的吸附是稳定的，Al掺杂后这种趋势仍然存在。在大多数情况下，Al削弱了表面和亚表面对N的吸附能力。吸附能分析表明，Al增强了解吸和吸附效率，从而从热力学角度促进了N的渗透。计算的侵彻路径结果进一步支持了这一趋势。本研究对钛表面氮化过程中Al掺杂剂的催化渗透机理提供了基础性的认识。

引用次数: 0

Covariance and the min-max principle in relativistic quantum chemistry: minimal basis Dirac-Fock calculations on atoms up to Z = 18 相对论量子化学中的协方差和最小-最大原理：Z = 18以下原子的最小基狄拉克-福克计算

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-10-25 DOI: 10.1016/j.comptc.2025.115562

Sambhu N. Datta

It was recently shown that the spinor obtained from the maximum step of min-max method has optimally constrained upper and lower components that restore Lorentz invariance in an average form [COMPTC, 1198 (2021) 113167; 1242 (2024) 114888]. Hence the maximum spinor completely lies within the subspace of bound state eigenfunctions. The same observation must hold for the eigenvectors and eigenfunctions of the relativistic Fock operator, as the four-component Dirac-Fock equations can be derived from a min-max procedure. An analytical proof of covariance and an analytical example are provided for maximum eigenvectors of atomic Fock operator. Spinors of the maximum type can be constructed and subsequently made the members of a covariant basis set for an efficient use in Dirac-Fock calculations. A numerical demonstration of covariance is given for the basis spinors as well as eigenvectors from optimized minimal-basis calculations on atoms with Z ≤ 18.

最近的研究表明，由最小-最大方法的最大步长得到的旋量具有最优约束的上下分量，它们以平均形式恢复洛伦兹不变性[COMPTC， 1198 (2021) 113167；[1242(2024) 114888]。因此最大旋量完全位于束缚态本征函数的子空间内。对于相对论性Fock算子的特征向量和特征函数，同样的观察结果必须成立，因为四分量Dirac-Fock方程可以从最小-最大过程中导出。给出了原子Fock算子最大特征向量的协方差的解析证明和解析实例。极大型旋量可以构造成协变基集的成员，从而在Dirac-Fock计算中得到有效的利用。对Z≤18原子的优化最小基计算给出了基旋量和特征向量的协方差的数值证明。

引用次数: 0

Janus XPbS2/XPbSe2 (X = Sn, Ge) heterostructures: Efficient direct Z-scheme photocatalysts for overall water splitting Janus XPbS2/XPbSe2 （X = Sn, Ge）异质结构：高效直接Z-scheme光催化剂

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-10-24 DOI: 10.1016/j.comptc.2025.115554

Zhigang Yu , Furong Xu , HengWang , Shiyu Xiao , Song Li , Zean Tian

Two-dimensional (2D) Janus materials have recently attracted significant attention for their potential applications in photocatalytic water splitting. In this work Janus XPbS₂/XPbSe₂ (X = Sn, Ge) heterostructures were investigated systematically by using first-principles calculations. It is found that these heterostructures have excellent kinetic stability, narrowed bandgaps, and significantly improved optical absorption (>10⁵ cm⁻¹) in both visible and ultraviolet regions. Electronic structure, band alignment, and built-in electric field analyses confirm their direct Z-scheme characteristics (with efficient separation of photogenerated carriers and enhanced redox abilities), beneficial for spontaneous overall water splitting. Strain engineering further enhances band-edge alignment and solar-to‑hydrogen efficiency η_STH, achieving up to 40 % at 5 % tensile strain. This study provides valuable theoretical guidance for designing efficient 2D heterojunction photocatalysts.

二维Janus材料因其在光催化水分解中的潜在应用而引起了人们的广泛关注。本文采用第一性原理计算方法系统地研究了Janus XPbS2/XPbSe2 （X = Sn, Ge）异质结构。研究发现，这些异质结构具有优异的动力学稳定性，窄小的带隙，显著提高了可见光和紫外区的光吸收（>105 cm−1）。电子结构、能带排列和内置电场分析证实了它们的直接Z-scheme特性（具有光生载流子的有效分离和增强的氧化还原能力），有利于自发的整体水分解。应变工程进一步提高了带边对准和太阳能-氢效率ηSTH，在5%的拉伸应变下达到40%。该研究为设计高效的二维异质结光催化剂提供了有价值的理论指导。

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引用次数: 0

Effect of Ta content on structural and elastic properties of binary Ta-W metallic glasses Ta含量对二元Ta- w金属玻璃结构和弹性性能的影响

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-10-24 DOI: 10.1016/j.comptc.2025.115558

A. Khmich, A. Samiri, A. Hasnaoui

This study investigates the structural and elastic properties of binary Ta-W metallic glasses (MGs) with varying compositions using molecular dynamics simulations and an Embedded-Atom Method potential. Structural characterization through radial distribution function (RDF), partial RDF (PRDF), and Voronoi tessellation analysis (VTA) revealed that increasing Ta content enhances the glass transition temperature (Tg), indicating improved thermal stability. RDF and PRDF analyses showed that Ta-rich alloys exhibit sharper peaks and RDF splitting, reflecting enhanced short-range and medium-range order. VTA identified dominant icosahedral-like clusters, which play a key role in glass formation and crystallization resistance. Coordination number (CN) analysis revealed a shift towards higher CN values during cooling, suggesting denser atomic packing. Elastic property analysis, including elastic constants (C₁₁, C₁₂, C₄₄), bulk modulus (B), shear modulus (G), and Poisson's ratio (ν), showed that higher Ta content increases plasticity (higher ν) while reducing hardness. These findings enable tailored design of Ta-W MGs for advanced applications.

本研究利用分子动力学模拟和嵌入原子法电位研究了不同成分的二元Ta-W金属玻璃的结构和弹性特性。通过径向分布函数（RDF）、部分RDF （PRDF）和Voronoi镶嵌分析（VTA）进行的结构表征表明，Ta含量的增加提高了玻璃化转变温度（Tg），表明热稳定性得到改善。RDF和PRDF分析表明，富ta合金表现出更尖锐的峰和RDF分裂，反映出增强的近程和中程秩序。VTA鉴定出主要的二十面体类团簇，它们在玻璃形成和抗结晶性中起关键作用。配位数（CN）分析显示，在冷却过程中，CN值向更高的方向转变，表明原子堆积更密集。弹性常数（C11、C12、C44）、体模量(B)、剪切模量(G)和泊松比（ν）分析表明，高Ta含量提高了塑性（ν），降低了硬度。这些发现使Ta-W mg的定制设计能够用于高级应用。

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引用次数: 0

The catalytic decomposition mechanism of hydroxylamine nitrate on the Ru(101) surface 硝酸羟胺在Ru（101）表面的催化分解机理

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-10-24 DOI: 10.1016/j.comptc.2025.115559

Yu Shen , Zihan Shi , Xiushuang Zhou , Xu Hu , Tianliang Yao , Yongmin Huang

To address the need for low-cost hydroxylamine nitrate (HAN) propellant decomposition catalysts, research was conducted to investigate the catalytic reaction mechanism of Ru-based catalysts. Quantum chemical calculation methods were employed to study the catalytic decomposition mechanism of HAN molecules on the Ru(101) surface. The research results show that HAN primarily adsorbs on the catalyst surface in the form of RuO bond. First, the NO bond in the NO₃⁻group of HAN undergoes cleavage, generating NO₂ and O. Subsequently, O reacts with NH₃OH, abstracting two H atoms to form NH₂O and H₂O. After the decomposition of HAN is completed, NH₂O and NO₂ undergo independent catalytic decomposition. For NH₂O, the process starts with the cleavage of the NO bond, ultimately forming N and H₂O, while for NO₂, the decomposition involves the detachment of O atoms, eventually transforming N and O.

针对低成本硝酸羟胺推进剂分解催化剂的需求，对钌基催化剂的催化反应机理进行了研究。采用量子化学计算方法研究了HAN分子在Ru（101）表面的催化分解机理。研究结果表明，HAN主要以若o键的形式吸附在催化剂表面。首先，HAN的NO3−基团中的NO键发生裂解，生成NO2和O。随后，O与NH3OH反应，抽出两个H原子生成NH2O和H2O。HAN分解完成后，NH2O和NO2独立催化分解。对于NH2O，分解过程从NO键的断裂开始，最终形成N和H2O，而对于NO2，分解过程包括O原子的脱离，最终转化为N和O。

引用次数: 0

Emerging potential chalcogenide perovskites BaHfX3 (X = S, Se) for energy conversion devices: Photovoltaic applications 用于能量转换装置的新兴潜在硫系钙钛矿BaHfX3 (X = S, Se)：光伏应用

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-10-22 DOI: 10.1016/j.comptc.2025.115556

Naincy Pandit , Rashmi Singh , Manendra S. Chauhan , Tarun Kumar Joshi , Anusha Dubey , Kulwinder Kaur , Rajeev Gupta , Tanuj Kumar , Samah Al-Qaisi , Ajay Singh Verma

Various properties of BaHfX₃ (X = S, Se) chalcogenide perovskites like structural, optical, phonon spectra, thermodynamic parameters along with the thermoelectric as well as electrical properties of these materials have been investigated. The Tran-Blaha modified Becke-Johnson potential (TB-mBJ) has been implemented for enhancing the accuracy in bandgap determination, as it yields more precise results for solid-state systems. These are semiconducting in nature disclosed by the band structure analysis. The observed results show good consistency with the available data. The dynamic stability of orthorhombic phase of BaHfX₃ (X = S and Se) compositions is verified through phonon calculation. The thermodynamic parameters at different temperature range 300 K to 800 K in which Dulong-Petit limit shows the phase stability and the elastic property calculations validate the mechanical robustness of these compounds. The Spectroscopic Limited Maximum Efficiency (SLME) study also illustrates that these materials are intriguing candidates for photovoltaic applications due to their performance, cost-effectiveness, and suitable bandgap.

研究了BaHfX3 （X = S, Se）硫系钙钛矿的结构、光学、声子光谱、热力学参数以及这些材料的热电和电学性能。trans - blaha改进的贝克-约翰逊电势（TB-mBJ）已被用于提高带隙测定的准确性，因为它可以为固态系统提供更精确的结果。这些都是半导体性质的揭示了带结构分析。观测结果与现有数据吻合较好。通过声子计算验证了BaHfX3 （X = S和Se）组合物正交相的动态稳定性。在300 ~ 800 K的不同温度范围内，化合物的热力学参数表现出相稳定性，其中Dulong-Petit极限表现出相稳定性，弹性性能计算证实了化合物的力学鲁棒性。光谱限制最大效率（SLME）研究还表明，由于其性能、成本效益和合适的带隙，这些材料是光伏应用的有趣候选者。

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引用次数: 0

Support's electronic structure tuning CO2 methanation on Ru4/TiO2 catalysts: A DFT study Ru4/TiO2催化剂上调控CO2甲烷化的载体电子结构：DFT研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-10-22 DOI: 10.1016/j.comptc.2025.115553

Boxin Cheng , Xiuzhong Fang , Meijuan Cao , Xiang Wang , Xianglan Xu

DFT calculations were used to examine how the electronic structure of TiO₂ supports affects CO₂ methanation on Ru₄ clusters. The electronic structure of nL-TiO₂ varies with the number of layers, and the binding ability of its two-coordinated surface oxygen atoms with metals differs. The 3 L-TiO₂ binds Ru₄ more strongly and obtains more electrons than 2 L-TiO₂, indicative of stronger metal-support interactions. Mechanistic analysis reveals that CO₂ methanation proceeds via competing CO* and HCOO* pathways on Ru₄/2 L-TiO₂, whereas the reaction through the HCOO* pathway on Ru₄/2 L-TiO₂ requires a substantially lower energy barrier. The origin of the alteration of the optimal pathway and the lower barrier is attributed to the stronger metal–support interactions weakening CO₂* adsorption on Ru₄/3 L-TiO₂ without comparable destabilization of the downstream intermediates compared to Ru₄/2 L-TiO₂. The results establish the electronic structure of oxide supports as a crucial factor for advanced CO₂ methanation catalysts.

采用DFT计算来考察TiO2载体的电子结构对Ru4簇上CO2甲烷化的影响。nL-TiO2的电子结构随层数的变化而变化，其表面双配位氧原子与金属的结合能力也不同。与2 L-TiO2相比，3 L-TiO2与Ru4的结合更强，获得更多的电子，表明其与金属载体的相互作用更强。机理分析表明，CO2甲烷化在Ru4/2 L-TiO2上通过CO*和HCOO*竞争途径进行，而在Ru4/2 L-TiO2上通过HCOO*途径进行的反应所需的能垒要低得多。与Ru4/2 L-TiO2相比，较强的金属-载体相互作用减弱了CO2在Ru4/3 L-TiO2上的吸附，而下游中间体不稳定。结果表明，氧化物载体的电子结构是先进的CO2甲烷化催化剂的关键因素。

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Revisiting the kinetics of pyridine pyrolysis. Part 1: H atom abstraction reactions 重温吡啶热解动力学。第一部分：氢原子萃取反应

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-10-21 DOI: 10.1016/j.comptc.2025.115555

Jibiao Xie , Anna S. Savchenkova , Alexander M. Mebel , Alexander A. Konnov

High-temperature decomposition of pyridine, C₅H₅N, occurs during waste incineration, pyrolysis of biomass and coal. In the present work, the rate constants of H atom abstraction from C₅H₅N by H, CH₃, CN, C₂H₃, CHCHCN and nC₄H₃ radicals have been calculated at the DLPNO-CCSD(T)-F12/cc-pVDZ-F12//M06-2X/def2-TZVP level of theory from 300 to 2000 K. The new rate constants obtained in the present work, in most cases are notably different from the expressions suggested in the earlier studies on pyridine pyrolysis or derived in theoretical calculations. Only for reactions of H atom abstraction by H, a reasonable agreement was found. It was revealed that the formation of ortho-, meta-, and para-pyridyls could be of equal importance and, therefore, all pyridyl isomers should be considered in detailed kinetic mechanisms for pyridine.

吡啶（C5H5N）在垃圾焚烧、生物质热解和煤热解过程中发生高温分解。本文在300 ~ 2000 K的DLPNO-CCSD(T)-F12/cc-pVDZ-F12//M06-2X/def2-TZVP理论水平上，计算了H、CH3、CN、C2H3、CHCHCN和nC4H3自由基从C5H5N中提取H原子的速率常数。在大多数情况下，本文得到的新的速率常数与以往的吡啶热解研究或理论计算中得到的表达式有明显的不同。只有在H原子被H抽离的反应中，才有较好的一致性。结果表明，邻位、间位和对吡啶的形成可能同样重要，因此，在详细的吡啶动力学机制中应考虑所有的吡啶异构体。

引用次数: 0

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