Computational and Theoretical Chemistry最新文献_第6页

Stimulating band gap reduction of AZnF3 (A = Ga, In) perovskites under external pressure for improving optoelectronic performance 在外部压力作用下激发 AZnF3（A = Ga、In）包晶带隙减小以改善光电性能

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-10-28 DOI: 10.1016/j.comptc.2024.114940

Md Saiduzzaman , Khandaker Monower Hossain , Arpon Biswas , Safin Alam , Aldina Sultana , Tanjun Ahmed , Jahid Kabir Rony , Sohail Ahmad , Mst.A. Khatun , S.K. Mitro

This study extensively examines the influence of pressure on several physical characteristics of cubic halide perovskites AZnF₃ (A = Ga, In) in extreme conditions (up to 60 GPa hydrostatic pressure) via the use of the first principles approach. The reduction of the band gap of the chosen compounds under increasing pressure is comprehensively discussed through the band structure and density of states calculations. The strong hybridization between Ga-4p(In-5p) and F-2p states under pressure is responsible for lowering the electronic band gap. The ionic and covalent nature of Ga/In–F and Zn–F bonds, respectively, are confirmed by charge density mapping. The optical absorption shifts towards lower energy regions under pressure are advantageous for using AZnF₃ (A = Ga, In) in photovoltaic applications. Furthermore, the comprehensive optical study demonstrates that the compound synthesized under pressure exhibits greater suitability for use in optoelectronic devices compared to systems formed under zero-pressure conditions. Interestingly, the brittleness of GaZnF₃ is converted to ductile under the application of pressure.

本研究通过使用第一原理方法，广泛研究了在极端条件下（高达 60 GPa 静水压力）压力对立方卤化物包光体 AZnF3（A = Ga、In）若干物理特性的影响。通过能带结构和态密度计算，全面讨论了所选化合物在压力增加时能带隙的减小。在压力作用下，Ga-4p（In-5p）态和 F-2p 态之间的强杂化是降低电子带隙的原因。电荷密度图分别证实了 Ga/In-F 和 Zn-F 键的离子和共价性质。在压力作用下，光吸收向低能区转移，这有利于在光伏应用中使用 AZnF3（A = Ga、In）。此外，全面的光学研究表明，与在零压条件下形成的体系相比，在压力下合成的化合物更适合用于光电器件。有趣的是，在施加压力的情况下，GaZnF3 的脆性转变为延展性。

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引用次数: 0

Interaction between Molnupiravir and noble metal substrates in SERS detection: A DFT method and Raman characteristic study SERS 检测中莫诺吡拉韦与贵金属基底的相互作用：DFT 方法和拉曼特性研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-10-24 DOI: 10.1016/j.comptc.2024.114926

Shuai Lian, Xiaoqiong Li , Xuefei Lv

Molnupiravir, a nucleoside analogue (EIDD-2801), is an RNA polymerase inhibitor that effectively treats infections caused by novel coronaviruses and can be administered orally. Therefore, it is necessary to monitor the distribution of Molnupiravir in vivo after oral administration. Surface-enhanced Raman spectroscopy (SERS) is a suitable detection method, so it is necessary to understand the interaction between Molnupiravir and noble metal nanoparticles in the SERS effect. Therefore, we used density functional theory combined with surface-enhanced Raman spectroscopy to investigate the interaction between Molnupiravir and noble metal/composite nanoparticles in the SERS effect. To study the interaction sites of Molnupiravir and the substrate in the SERS effect, the molecular electrostatic potential (MEP) of Molnupiravir was calculated. Considering the significant role of binding energy in studying molecular docking, the binding energy between Molnupiravir and Metal₆ (Au₆, Ag₆, Au₃Ag₃) atomic clusters was calculated. The calculated results of the frontier orbitals and relevant molecular parameters of Molnupiravir and Molnupiravir-Metal₆ complexes reveal the changes in the molecular properties of Molnupiravir in the SERS effect. Finally, the theoretical Raman spectra differences between Molnupiravir and complexes were compared and analyzed, and the adsorption structure of Molnupiravir on the substrate surface was determined based on the surface selection rules of SERS. The research results will provide insights into the interaction between Molnupiravir and the substrate in the SERS effect, and also offer theoretical support for the application of SERS methods in biomedical detection.

Molnupiravir是一种核苷类似物（EIDD-2801），是一种RNA聚合酶抑制剂，可有效治疗新型冠状病毒引起的感染，并可口服给药。因此，有必要监测莫能吡韦口服后在体内的分布情况。表面增强拉曼光谱（SERS）是一种合适的检测方法，因此有必要了解SERS效应中莫能吡韦与贵金属纳米颗粒之间的相互作用。因此，我们采用密度泛函理论结合表面增强拉曼光谱研究了SERS效应中莫能吡韦与贵金属/复合纳米粒子之间的相互作用。为了研究SERS效应中莫能吡韦与基底的相互作用位点，计算了莫能吡韦的分子静电位（MEP）。考虑到结合能在分子对接研究中的重要作用，计算了莫能吡韦与金属 6（Au6、Ag6、Au3Ag3）原子团簇之间的结合能。莫能吡韦和莫能吡韦-金属 6 复合物的前沿轨道和相关分子参数的计算结果揭示了莫能吡韦在 SERS 效应中分子性质的变化。最后，比较分析了莫能吡韦与配合物的理论拉曼光谱差异，并根据 SERS 的表面选择规则确定了莫能吡韦在基底表面的吸附结构。这些研究成果将有助于深入了解SERS效应中莫能吡韦与基底之间的相互作用，也为SERS方法在生物医学检测中的应用提供了理论支持。

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引用次数: 0

Model study on potential removal of toxic Se(VI) by organically modified montmorillonite 有机改性蒙脱石去除有毒硒(VI)潜力的模型研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-10-24 DOI: 10.1016/j.comptc.2024.114939

Peter Škorňa , Sanam Bashir , Eva Scholtzová , Daniel Tunega

The theoretical DFT-D3 approach was used in the model study of the immobilisation of the toxic selenate oxyanion, with montmorillonite clay modified by poly(2-methyl-2-oxazoline) polymer represented by a pentamer unit, and tetrabutylphosphonium cation. The calculated basal spacing for Se-POx-Mt and Se-TBP-Mt models provided similar results differing by 0.2 Å (18.3 Å for Se-POx-Mt and/or 18.5 Å for Se-TBP-Mt, respectively). The calculated intercalation energy, ΔE_int, showed a suitability of both modified Mts for trapping of (SeO₄)^2– oxyanions favouring the Se-TBP-Mt (–210.7 kJ/mol) system compared to Se-POx-Mt (–124.5 kJ/mol). The main interactions in both models were classified as hydrogen bonds of weak (CH···O) and moderate-to-strong (OH···O) strength. The calculated total and projected vibrational density of states of the Se-POx-Mt and Se‑TBP‑Mt models, obtained from the ab initio molecular dynamics simulations, were used for distinct identification of vibrational modes of the intercalated (SeO₄)^2– ion in the interlayer space of both models.

理论 DFT-D3 方法用于有毒硒酸氧阴离子的固定化模型研究，蒙脱石粘土由五聚体单元代表的聚（2-甲基-2-噁唑啉）聚合物和四丁基鏻阳离子修饰。Se-POx-Mt 和 Se-TBP-Mt 模型的基底间距计算结果相似，相差 0.2 Å（Se-POx-Mt 和/或 Se-TBP-Mt 分别为 18.3 Å 和/或 18.5 Å）。计算得出的插层能ΔEint 显示，两种改性锰元素都适合捕获 (SeO4)2- 氧阴离子，与 Se-POx-Mt （-124.5 kJ/mol）相比，Se-TBP-Mt（-210.7 kJ/mol）系统更适合捕获 (SeO4)2- 氧阴离子。两种模型中的主要相互作用被归类为弱（CH--O）和中-强（OH--O）氢键。通过ab initio分子动力学模拟计算得到的Se-POx-Mt和Se-TBP-Mt模型的总振动态密度和投影振动态密度，用于识别这两种模型层间空间中插层（SeO4）2-离子的振动模式。

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引用次数: 0

A study on the properties of chloroquine and hydroxychloroquine derivatives as biomass corrosion inhibitors 氯喹和羟基氯喹衍生物作为生物质缓蚀剂的特性研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-10-24 DOI: 10.1016/j.comptc.2024.114938

Rebaz Obaid Kareem , Rebaz Anwar Omer , Yousif Hussein Azeez , Lana Omer Ahmed , Othman Abdulrahman Hamad

Since corrosion causes significant economic and environmental damage, sustainable corrosion inhibitors are essential. This work examined the corrosion prevention properties of a series of closely related compounds with names: Chloroquine (S1) Hydroxychloroquine (S2) Desethylchloroquine (S3) Desethylhydroxychloeoquine (S4) Bisdesethylchloroquine (S5). With applying DFT/B3LYP/6-31+G(d,p) foundation, also Monte Carlo simulations showed compound adsorption on Fe(1 1 0). The HOMO-LUMO, refractive index, dielectric constant, and electrical conductivity, the results for S1 and S2 indicate that all inhibitors were bound to Fe (1 1 0), as predicted by the Monte Carlo simulation.

由于腐蚀会对经济和环境造成重大损害，因此必须使用可持续的缓蚀剂。这项工作研究了一系列名称密切相关的化合物的防腐蚀性能：氯喹（S1）、羟基氯喹（S2）、去乙基氯喹（S3）、去乙基羟基氯喹（S4）、双去乙基氯喹（S5）。在 DFT/B3LYP/6-31+G(d,p) 基础上，蒙特卡罗模拟也显示了化合物在 Fe(1 1 0) 上的吸附情况。S1 和 S2 的 HOMO-LUMO、折射率、介电常数和电导率结果表明，正如蒙特卡罗模拟所预测的那样，所有抑制剂都与铁（1 1 0）结合。

引用次数: 0

The interaction between beta-ionone and 2-hydroxypropyl-beta-cyclodextrin during the formation of the inclusion complex beta-ionone 和 2-hydroxypropyl-beta-cyclodextrin 在形成包涵复合物过程中的相互作用

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-10-23 DOI: 10.1016/j.comptc.2024.114937

Xuliang Zhu , Guangyong Zhu

As an aroma material, beta-ionone also has a range of pharmacological activities. To solve its problems such as low bioavailability, water-immiscibility, thermo-instability, and volatility, beta-ionone was successfully encapsulated in 2-hydroxypropyl-beta-cyclodextrin (HP-beta-CD) in our previous work. However, the structure of the product, the interaction between beta-ionone and HP-beta-CD, and the mechanism of action were not clear. In this paper, in order to gain a more profound understanding of the structure and chemical behavior of beta-ionone-HP-beta-CD inclusion complex, the interaction between beta-ionone and HP-beta-CD was investigated by molecular simulation. The optimized structures, binding energy, deformation energy, charge transfer, frontier orbital energy gap, chemical hardness, chemical potential, and electrophilicity index were obtained. In the complex, beta-ionone denotes electrons to HP-beta-CD and carries a positive charge. The negative chemical potential of inclusion complex indicates that complex process is spontaneous. The complex shows a relatively higher reactivity and electrophilicity than beta-ionone and HP-beta-CD.

作为一种芳香材料，β-酮还具有一系列药理活性。为了解决其生物利用度低、水溶性差、热不稳定性和挥发性等问题，我们在之前的研究中成功地将 beta-ionone 封装在 2-hydroxypropyl-beta-cyclodextrin (HP-beta-CD) 中。然而，该产品的结构、β-酮与 HP-beta-CD 之间的相互作用以及作用机制尚不清楚。为了更深入地了解β-酮-HP-β-CD包合物的结构和化学行为，本文通过分子模拟研究了β-酮与HP-β-CD之间的相互作用。通过分子模拟研究了β-酮与 HP-beta-CD 之间的相互作用，获得了优化的结构、结合能、变形能、电荷转移、前沿轨道能隙、化学硬度、化学势和亲电指数。在复合物中，β-酮向 HP-beta-CD 提供电子，并带有正电荷。包合络合物的化学势为负，表明络合过程是自发的。该复合物的反应活性和亲电性相对高于 beta-ionone 和 HP-beta-CD。

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引用次数: 0

Computational insights into the photophysical processes of an acylhydrazone fluorescent probe based on conical intersection and sensing mechanism for Al3+ detection 基于锥形交点的酰基腙荧光探针的光物理过程和 Al3+ 检测传感机制的计算见解

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-10-23 DOI: 10.1016/j.comptc.2024.114934

Pengcheng Zhang , Chunxiang Zhao , Hongyu Chen , Han Zhang , Huijie Ni , Yubing Si

Al³⁺ detection is crucial for food safety, environmental monitoring, and biological assays. This work investigated the fluorescent properties of the probe VN62 and its sensing mechanism for the detection of Al³⁺ ion in detail. The ground- and excited-state properties such as isomerization geometries and absorption spectra, as well as the photophysical processes of transitions in PES have been studied. There are few fluorescent S₁ states (PT*, TICT) of the VN62 molecule, and the conical intersections (CIs) have key importance in the fluorescent process. By comparing the radiative rate (k_r) and the rate of transition to CI, we deduce that these fluorescent states are lack of stability for light emission. Therefore, the fluorescence of probe alone can be quenched by CI pathways. After coordination with Al³⁺, the CI pathways will be suppressed, resulting in enhanced fluorescence. This sensing mechanism is different from the previously proposed mechanisms, such as the dark state of TICT or ESIPT. We anticipate that our research would shed some light on the design of turn-on sensors.

Al3+ 检测对食品安全、环境监测和生物检测至关重要。这项工作详细研究了探针 VN62 的荧光特性及其检测 Al3+ 离子的传感机制。研究了 PES 的基态和激发态特性，如异构化几何形状和吸收光谱，以及跃迁的光物理过程。VN62 分子中存在少数荧光 S1 态（PT*、TICT），而锥形交叉点（CI）在荧光过程中具有关键意义。通过比较辐射率（kr）和向 CI 过渡的速率，我们推断出这些荧光态缺乏光发射的稳定性。因此，探针本身的荧光可以通过 CI 途径被淬灭。与 Al3+ 配位后，CI 途径将被抑制，从而导致荧光增强。这种传感机制不同于之前提出的机制，如 TICT 或 ESIPT 的暗态。我们希望我们的研究能为开启传感器的设计提供一些启示。

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引用次数: 0

Theoretical insights into efficient electrocatalysts for nitrogen reduction reaction by transition metal atoms supported on g-C3N4 过渡金属原子在 g-C3N4 上支撑的高效氮还原反应电催化剂的理论见解

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-10-22 DOI: 10.1016/j.comptc.2024.114932

Pengfei Ma , Rui Wang , Chengsong Liu , Pengfei Liu , Chaozheng He , Wei Song , Tao Zhang

NH₃ is considered one of the most important chemicals, not only as an industrial feedstock for the production of fertilizers, but also as renewable carbon-free energy carrier. In recent years, electrocatalytic nitrogen reduction reaction (NRR), which uses N₂ and H₂O as raw materials to synthesize NH₃, is considered as one of the most promising methods for N₂ fixation. Therefore, the design and synthesis of NRR electrocatalysts with high catalytic performance is very important. Herein, using density functional theory method, 3d transition metal single atom anchored to g-C₃N₄ as single-atom catalysts was studied for the catalytic reduction of N₂. The results found that V@g-C₃N₄ exhibited high electrocatalytic activity and good catalytic selectivity. The limiting potential was only –0.115 V. Furthermore, the relevant electronic properties of V@g-C₃N₄ were also analyzed. Our work can provide ideas and help to understand the reaction mechanism of single atom doped g-C₃N₄ as NRR electrocatalysts with excellent catalytic performance.

NH3 被认为是最重要的化学物质之一，不仅是生产肥料的工业原料，还是可再生的无碳能源载体。近年来，以 N2 和 H2O 为原料合成 NH3 的电催化氮还原反应（NRR）被认为是最有前途的 N2 固定方法之一。因此，设计和合成具有高催化性能的氮还原反应电催化剂非常重要。本文利用密度泛函理论方法，研究了锚定在 g-C3N4 上的 3d 过渡金属单原子作为单原子催化剂催化还原 N2 的情况。结果发现，V@g-C3N4 具有很高的电催化活性和良好的催化选择性。此外，还分析了 V@g-C3N4 的相关电子特性。我们的工作为理解单原子掺杂 g-C3N4 作为具有优异催化性能的 NRR 电催化剂的反应机理提供了思路和帮助。

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引用次数: 0

Effects of metals (X = Pd, Ag, Cd ) on structural, electronic, mechanical, thermoelectric and hydrogen storage properties of LiXH3 perovskites 金属（X = Pd、Ag、Cd）对 LiXH3 包晶的结构、电子、机械、热电和储氢特性的影响

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-10-21 DOI: 10.1016/j.comptc.2024.114927

Anupam , Shyam Lal Gupta , Sumit Kumar , Samjeet Singh Thakur , Ashwani Kumar , Sanjay Panwar , Diwaker

Using the WIEN2K code, the hydrogen storage capabilities of lithium compositions like LiXH3 (X = Pd, Ag, Cd) hydrides are examined. Structural, electronic, mechanical, thermoelectric, and hydrogen storage properties of these hydrides are analyzed using first-principles simulations. Structural analysis of these compositions reveals that the hydrides are stable and belong to the cubic space group number (221 Pm-3 m). The thermodynamic stability of these hydrides are given in terms of formation energies and stability is checked through phonon dispersion curves. The purpose of the study is to calculate formation energy and breakdown temperature to determine stability of these hydrides. The metallic nature of all compositions are confirmed by band plots and density of states. The elastic properties are calculated to check the applicability of these compositions for applications involving hydrogen storage. The present paper represents the initial theoretical approach towards the future exploration of these materials for hydrogen storage applications.

利用 WIEN2K 代码研究了 LiXH3（X = Pd、Ag、Cd）氢化物等锂成分的储氢能力。利用第一原理模拟分析了这些氢化物的结构、电子、机械、热电和储氢特性。对这些成分的结构分析表明，这些氢化物是稳定的，属于立方空间群（221 Pm-3 m）。这些氢化物的热力学稳定性以形成能量的形式给出，并通过声子频散曲线检验其稳定性。研究的目的是计算形成能和击穿温度，以确定这些氢化物的稳定性。通过带图和状态密度确认了所有成分的金属性质。还计算了弹性特性，以检查这些成分在储氢应用中的适用性。本文代表了未来探索这些材料储氢应用的初步理论方法。

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引用次数: 0

Elucidation of the influence of trinitro-diazinotriazine isomerism on the energetic properties and stability: Insights from DFT approach 阐明三硝基迭嗪三嗪异构体对能量特性和稳定性的影响：DFT 方法的启示

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-10-20 DOI: 10.1016/j.comptc.2024.114931

Kalpana Sharma , Rimpi Devi , Vikas D. Ghule , Srinivas Dharavath

The exploration of isomeric energetic molecules with high nitrogen content and the examination of their structure–property relationships remains compelling areas of interest within the field of energetic materials. Energetic isomers comprising the same molecular composition but distinct molecular structures potentially lead to notable variations in performance and properties. This study focused on designing and evaluating different forms of diazinotriazine using two molecular compositions: C₅H₃N₅ and C₅N₈O₆, aiming to generate various isomeric structures and to guide the rational design of new molecules. The electronic configurations, energetic properties, and sensitivity prediction of the optimized structures were investigated using the M06-2X/def2-TZVPP level of theory. The trinitro-diazinotriazine isomers exhibit high heat of formation (>486 kJ/mol), high detonation properties (D > 8.7 km/s, P > 34 GPa), high density (>1.81 g/cm³), and better thermal stability (BDE > 230 kJ/mol) making them promising explosive contenders. Among the designed diazinotriazine backbones, the pyridazine-1,2,3-triazine framework is favourable for the heat of formation and detonation properties. The heats of formation, detonation velocity, pressure, and heats of detonation of A4 and B4 outperform the other trinitro-diazinotriazine isomers.

探索含氮量高的高能分子异构体并研究其结构与性能的关系，仍然是高能材料领域引人关注的领域。由相同分子组成但分子结构不同的高能异构体可能会导致性能和特性的显著变化。本研究的重点是利用两种分子组成设计和评估不同形式的重氮三嗪：C5H3N5 和 C5N8O6，旨在生成各种异构体结构并指导新分子的合理设计。采用 M06-2X/def2-TZVPP 理论水平研究了优化结构的电子构型、能量特性和灵敏度预测。三硝基重氮三嗪异构体表现出高形成热（486 kJ/mol）、高引爆性能（D 8.7 km/s，P 34 GPa）、高密度（1.81 g/cm3）和更好的热稳定性（BDE 230 kJ/mol），使它们成为有前途的爆炸物竞争者。在所设计的重氮三嗪骨架中，哒嗪-1,2,3-三嗪骨架在形成热和引爆特性方面是有利的。A4 和 B4 的形成热、起爆速度、压力和起爆热均优于其他三硝基二氮三嗪异构体。

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引用次数: 0

Adsorption of methane and carbon dioxide on boron, aluminum, and gallium-coordinated ortho-phenylene-bridged cyclic pyrrole complexes 甲烷和二氧化碳在硼、铝和镓配位的邻苯基桥环吡咯络合物上的吸附作用

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2024-10-20 DOI: 10.1016/j.comptc.2024.114928

Marisol Ibarra-Rodríguez , Adalid Armenta , Mario Sánchez

In this study, we explored the adsorption properties of methane (CH₄) and carbon dioxide (CO₂) on ortho-phenylene-bridged cyclic pyrrole (OPBCP) complexes coordinated with boron (B), aluminum (Al), and gallium (Ga) atoms. Our computational results reveal that the adsorption energies (E_ads) for a single molecule of CH₄ or CO₂ range from −4.09 to −17.89 kcal/mol. When two molecules are absorbed, one either side of the complex, the energies range from −8.32 to −26.01 kcal/mol. Theoretical calculations were performed using the Perdew-Burke-Ernzerhof (PBE0) functional and the def2-TZVP basis set, with further refinement through single-point calculations at the CCSD(T)-DLPNO level of theory, also employing the def2-TZVP auxiliary basis set. Additionally, moderate back-donation is observed in the Al-OPBCP and Ga-OPBCP complexes, where electron density is redistributed from the metal centers to both the OPBCP framework and the gas molecules. This makes them promising candidates for applications in gas separation and capture technologies.

在这项研究中，我们探讨了甲烷（CH4）和二氧化碳（CO2）在与硼（B）、铝（Al）和镓（Ga）原子配位的正交苯桥环状吡咯（OPBCP）络合物上的吸附特性。我们的计算结果显示，单分子 CH4 或 CO2 的吸附能 (Eads) 在 -4.09 至 -17.89 kcal/mol 之间。当吸附两个分子（复合物的一侧和另一侧）时，能量范围为 -8.32 至 -26.01 kcal/mol。理论计算使用了 Perdew-Burke-Ernzerhof (PBE0) 函数和 def2-TZVP 基础集，并通过在 CCSD(T)-DLPNO 理论水平上的单点计算（也使用了 def2-TZVP 辅助基础集）进一步完善。此外，在 Al-OPBCP 和 Ga-OPBCP 复合物中观察到了适度的反奉献现象，电子密度从金属中心重新分配到 OPBCP 框架和气体分子中。这使得它们有望应用于气体分离和捕获技术。

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引用次数: 0