Computational and Theoretical Chemistry最新文献_第2页

The reactive fingerprint of toxic alkylphenols: Insights from NO+ chemical ionization and spectroscopy 有毒烷基酚的反应指纹图谱：来自NO+化学电离和光谱学的见解

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-01-15 DOI: 10.1016/j.comptc.2026.115682

Manjeet Bhatia

Alkylphenols, which consist of a phenolic ring attached to an alkyl chain, are widely used in industrial processes and consumer products, including food-contact materials such as plastic containers. Their broad application raises concerns regarding human exposure and environmental impact. In this work, density functional theory (DFT) was employed to investigate the electronic structure and chemical reactivity of alkylphenols using different DFT functionals. The key molecular descriptors, including ionization energy, electron affinity, HOMO–LUMO gap, and global reactivity parameters, were systematically evaluated. Excited-state properties and UV–Vis absorption spectra were further examined through time-dependent DFT (TD-DFT). The potential of NO

^{+}

as a reagent ion was also explored through charge transfer and H

^{-}

abstraction reactions. Benchmark DFT calculations confirm that B3LYP/6-311++G(d, p) is well-suited for ground-state studies, and further evaluations demonstrate that NO

^{+}

readily undergoes exothermic charge transfer with alkylphenols, proceeding at collision-controlled rates. In contrast, hydride abstraction is endothermic, and association pathways are not favorable. These findings underscore the potential of NO

^{+}

-based chemical ionization mass spectrometry (CIMS) techniques, such as PTR-MS and SIFT-MS, for the sensitive detection and quantification of alkylphenols. Overall, this comprehensive computational study provides valuable insights into the stability, reactivity, and photophysical behavior of alkylphenols, advancing their identification in both environmental monitoring and human health risk assessments.

烷基酚由一个附着在烷基链上的酚环组成，广泛用于工业过程和消费品，包括塑料容器等与食品接触的材料。它们的广泛应用引起了人们对人类暴露和环境影响的担忧。本文采用密度泛函理论（DFT）研究了不同DFT官能团的烷基酚的电子结构和化学反应性。系统评价了关键分子描述符，包括电离能、电子亲和、HOMO-LUMO间隙和整体反应性参数。通过时间相关DFT （TD-DFT）进一步研究了激发态性质和紫外-可见吸收光谱。通过电荷转移和H -萃取反应，探讨了NO+作为试剂离子的潜力。基准DFT计算证实，B3LYP/6-311++G（d, p）非常适合基态研究，进一步的评估表明，NO+很容易与烷基酚进行放热电荷转移，并以碰撞控制的速率进行。相反，氢化物的提取是吸热的，结合途径是不利的。这些发现强调了基于NO+的化学电离质谱（CIMS）技术，如PTR-MS和SIFT-MS，在灵敏检测和定量烷基酚方面的潜力。总的来说，这项全面的计算研究为烷基酚的稳定性、反应性和光物理行为提供了有价值的见解，促进了它们在环境监测和人类健康风险评估中的识别。

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引用次数: 0

Layer-dependent band-gap evolution and convergence in R-TiO₂(110) surfaces r- tio2（110）表面的带隙演化与收敛

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-01-15 DOI: 10.1016/j.comptc.2026.115680

Jiahui Wu , Xinyu Xie , Yunxiang He , Yutong Zhang , Caifang Han , Dandan Wang , Hongwei Li , Ruimin Wang

The surface electronic structure of titanium dioxide governs its photocatalytic performance, but the depth of surface effects and the minimum reliable slab thickness remain uncertain. We systematically study rutile TiO₂(110) slabs (10–36 layers) using first-principles calculations. The local band gap evolves in a distinct “W”-shaped profile. Its minimum shifts inward with thickness and converges at the 8th atomic layer for slabs ≥30 layers, defining the surface-to-bulk transition. The valence band maximum arises from inner-layer O 2p orbitals, while the conduction band minimum is dominated by near-surface Ti 3d orbitals. An odd/even layer-number oscillation is also identified. This work establishes ≥30 layers (∼6 nm) as the critical thickness for accurately capturing surface electronic properties and ensuring bulk convergence. These results offer a quantitative model-selection benchmark and atomic-scale insight into surface evolution, aiding the design of optimized TiO₂ devices via surface engineering.

二氧化钛的表面电子结构决定了其光催化性能，但表面效应的深度和最小可靠板厚度仍然不确定。我们系统地研究金红石tio2（110）板（10-36层）使用第一性原理计算。局部带隙演变成一个明显的“W”形轮廓。对于≥30层的平板，其最小值随厚度向内移动，并在第8原子层收敛，定义了表面到块体的转变。价带最大值来自于内层的o2p轨道，而导带最小值主要来自于近表面的Ti 3d轨道。还发现了奇/偶层数振荡。这项工作确定了≥30层（~ 6 nm）作为精确捕获表面电子特性和确保整体收敛的临界厚度。这些结果提供了定量的模型选择基准和原子尺度的表面演变，有助于通过表面工程设计优化的tio2器件。

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引用次数: 0

Ab initio study of lead-free K₂ScInX₆ (X = F, Cl, Br, I) halide double perovskites for sustainable optoelectronics 无铅K₂ScInX₆（X = F, Cl, Br， I）卤化物双钙钛矿的从头算研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-01-14 DOI: 10.1016/j.comptc.2026.115681

Tanvir Al Galib , Ajadi Yasmen , Ahmad Irfan , Aijaz Rasool Chaudhry , Md. Atikur Rahman , Md. Faruk Hossain , Md. Ferdous Rahman

Lead-free halide double perovskites K₂ScInX₆ (X = F, Cl, Br, I) are systematically investigated using first-principles DFT to assess their suitability for optoelectronic applications. All compositions crystallize in the cubic Fm-3m phase with increasing lattice constants from F to I. Tolerance and octahedral factors, together with negative formation energies and phonon spectra free of imaginary modes, confirm structural, thermodynamic, and dynamical stability, with K₂ScInCl₆ exhibiting optimal geometric stability. Electronic calculations reveal direct band gaps at the L-point, tunable via halide substitution. Band gaps range from the visible to near-infrared, refined by SOC and HSE06 treatments. Mechanical analysis satisfies Born stability criteria, showing ductile behavior for Cl-based compounds and higher stiffness for F-based ones. Optical properties demonstrate strong dielectric response, efficient absorption, and increasing refractive index from F to I. Overall, K₂ScInX₆ emerges as a stable, lead-free, and optically versatile material family for photovoltaic and optoelectronic devices.

利用第一性原理DFT对无铅卤化物双钙钛矿K₂ScInX₆（X = F, Cl, Br， I）进行了系统的研究，以评估其在光电应用中的适用性。所有成分均在立方Fm-3m相结晶，晶格常数从F到i逐渐增大。公差和八面体因素，加上负的形成能和无赝模的声子谱，确定了结构、热力学和动力学稳定性，其中K₂ScInCl₆表现出最佳的几何稳定性。电子计算揭示了l点的直接带隙，可通过卤化物替代进行调节。带隙范围从可见光到近红外，经过SOC和HSE06处理。力学分析满足Born稳定性准则，表明cl基化合物具有延展性，f基化合物具有较高的刚度。光学性能表现出强烈的介电响应，有效的吸收，以及从F到i的折射率增加。总的来说，K₂ScInX₆是一种稳定，无铅，光学用途广泛的光伏和光电子器件材料系列。

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引用次数: 0

Size-dependent evolution in the geometry and electronic properties of Cs3Aln−/0 (n = 3–14) clusters Cs3Aln−/0 （n = 3-14）簇的几何和电子性质随尺寸的演化

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-01-11 DOI: 10.1016/j.comptc.2026.115661

Kai Wang , Chaoyong Wang , Linyuan Lian , Shuai Xu

The geometric structures, and electronic properties of Cs₃Al_n^−/0 (n = 3–14) clusters are investigated by using a hybrid global optimization algorithm combined with density functional theory (DFT) calculations. Based on the reported photoelectron spectra, the ground-state structures of Cs₃Al_n^−/0 (n = 8–14) anion clusters were identified. In these anionic and neutral clusters, all the three Cs atoms act as electron donors adsorbed on the Al_n framework, except in Cs₃Al₃⁻ and Cs₃Al₄⁻. The geometric structures of anionic and neutral clusters are generally consistent, except for sizes n = 3, 5, 7, 9, and 14. Binding energy analysis indicates that the average binding energy of Cs_mAl_n^−/0 clusters increases with cluster size but decreases with the number of Cs atoms. Among them, Cs₃Al₈⁻ and Cs₃Al₁₂⁻ exhibit pronounced HOMO–LUMO gaps and high second-order energy differences, which are attributed to their dual σ- and π-aromaticity.

采用混合全局优化算法结合密度泛函理论（DFT）计算研究了Cs3Aln−/0 （n = 3-14）簇的几何结构和电子性质。根据已报道的光电子能谱，确定了Cs3Aln−/0 （n = 8-14）阴离子簇的基态结构。在这些阴离子簇和中性簇中，除了Cs3Al3−和Cs3Al4−外，所有三个Cs原子都作为电子给体吸附在Aln骨架上。除了尺寸n = 3、5、7、9和14外，阴离子簇和中性簇的几何结构基本一致。结合能分析表明，CsmAln−/0簇的平均结合能随簇的大小而增大，随Cs原子数的增加而减小。其中，Cs3Al8−和Cs3Al12−表现出明显的HOMO-LUMO间隙和较高的二阶能差，这是由于它们具有σ-和π-双芳构性。

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引用次数: 0

A DFT study on the antioxidant mechanism of hibiscetin against the scavenging of hydroxyl and hydroperoxyl radicals 木糖素抗氧化机制的DFT研究清除羟基和羟基自由基

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-01-11 DOI: 10.1016/j.comptc.2026.115665

C. Ragi, G.S. Gopika Krishnan, K. Muraleedharan

The DFT/M062X/6–311 + G(d,p) approach was used in this study to examine thermodynamic characteristics of reactions related to potential antioxidant mechanisms of the flavonol hibiscetin against •OH and •OOH radicals in the gas and aqueous medium. Stationary points along the reaction pathways within the HAT (Hydrogen Atom Transfer) and RAF (Radical Adduct Formation) mechanisms were identified in the gas phase. Kinetic parameters such as reaction energy barriers and rate constants were also determined. According to the spin density distribution of the transition state structures and the free energy profile of the HAT pathways, 8-OH and 4’-OH are the most favoured sites of hibiscetin for radical attack. It is discovered that both the hydroxyl radical and hydroperoxyl radical assaults can occur via both the HAT and RAF routes, with 8-OH being the most preferred attacking site followed by 4’-OH.

本研究采用DFT/M062X/ 6-311 + G（d,p）方法研究了黄酮醇木糖素在气体和水介质中对•OH和•OOH自由基的潜在抗氧化机制相关反应的热力学特征。在气相中，确定了HAT（氢原子转移）和RAF（自由基加合物形成）反应路径中的固定点。测定了反应能垒和反应速率常数等动力学参数。根据过渡态结构的自旋密度分布和HAT途径的自由能分布，8-OH和4 ' -OH是芙蓉素最有利于自由基攻击的位点。发现羟基自由基和羟基过氧自由基的攻击均可通过HAT和RAF途径发生，8-OH是首选的攻击位点，其次是4 ' -OH。

引用次数: 0

Structural evolution and thermodynamic tuning of Sr₁₋ₓBaₓLiH₃: Inverse perovskites for high-volumetric-capacity hydrogen storage Sr₁₀ₓBaₓLiH₃：大容量储氢用逆钙钛矿的结构演化与热力学调整

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-01-11 DOI: 10.1016/j.comptc.2026.115663

S. Saadoun , T. Ghellab , H. Baaziz , T. Saadi , Z. .Charifi

This computational study investigates the structure-property relationships in Sr₁₋ₓBaₓLiH₃ (0 ≤ x ≤ 1) inverse perovskite hydrides using DFT. We demonstrate how controlled Ba substitution systematically tunes formation energies (−60.4 to −58.8 kJ/mol·H₂) and hydrogen binding energies (−1.19 to −1.24 eV), enabling precise optimization of hydrogen storage performance. The alloys exhibit an unusual structural evolution from cubic (

Pm \bar{3} m

) to tetragonal (P4/mmm) and back to cubic (

Pm \bar{3} m

) symmetry, with the re-entrant cubic phase at x = 0.875 showing exceptional stability (cohesive energy −17.1 eV). Electronic structure calculations reveal composition-dependent bandgap transitions (3.45–4.13 eV, mBJ-GGA) that alternate between direct and indirect character. For hydrogen storage, the materials' key advantage lies in their outstanding volumetric capacity of 188 g H₂/L, which significantly exceeds the capacities of many benchmark storage systems, while they maintain a moderate gravimetric capacity of 2.1–3.2 wt%. Desorption temperatures (449–462 K) are directly correlated with the hydrogen binding energy landscape. The study identifies an optimal composition window (x = 0.25–0.5) that balances favorable formation energy (−59.5 kJ/mol·H₂), moderate hydrogen binding (−1.22 eV), and robust thermodynamic stability. These findings establish a quantitative framework for designing perovskite hydrides with tailored hydrogen storage properties through controlled cation substitution, specifically targeting applications where high volumetric density is a critical requirement.

本计算研究利用DFT研究了Sr₁₃ₓBaₓLiH₃（0≤x≤1）逆钙钛矿氢化物的结构-性质关系。我们展示了受控Ba取代如何系统地调节形成能（- 60.4至- 58.8 kJ/mol·H₂）和氢结合能（- 1.19至- 1.24 eV），从而精确优化储氢性能。合金表现出不同寻常的结构演变，从立方（Pm3¯m）到四方（P4/mmm）再到立方（Pm3¯m）对称，其中在x = 0.875处重新进入的立方相表现出优异的稳定性（内聚能- 17.1 eV）。电子结构计算揭示了组分相关的带隙跃迁（3.45-4.13 eV, mBJ-GGA）在直接和间接特征之间交替。对于储氢，该材料的关键优势在于其出色的体积容量为188 g H₂/L，大大超过了许多基准储氢系统的容量，同时它们保持了2.1-3.2 wt%的中等重量容量。解吸温度（449 ~ 462 K）与氢结合能的变化直接相关。该研究确定了一个最佳组成窗口（x = 0.25-0.5），平衡了有利的地层能量（- 59.5 kJ/mol·H₂）、适度的氢键（- 1.22 eV）和强大的热力学稳定性。这些发现为通过控制阳离子取代设计具有定制储氢性能的钙钛矿氢化物建立了定量框架，特别是针对高体积密度是关键要求的应用。

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引用次数: 0

Theoretical study on the oxidative decomposition mechanism of 3,3,4,4,4-pentafluoro-1-butene 3,3,4,4,4-五氟丁烯氧化分解机理的理论研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-01-10 DOI: 10.1016/j.comptc.2026.115674

Miao Shi , Biao Feng , Bingrui Wang , Siqi Li , Jingjing Li , Yujing Guo , Jia Wu , Lin Wang , Suxia Ma , Dan Wang

As a low global warming potential hydrofluoroolefin, 3,3,4,4,4-pentafluoro-1-butene contains a double bond that raises concerns about its thermal stability, thus limiting its practical application in refrigeration. This study employed density functional theory to investigate its oxidative decomposition mechanism, exploring a total of 50 reaction pathways. These findings reveal that during initial thermal decomposition, the terminal CC bond in the -CF₃ group cleaves most readily, while the terminal CF bond requires the highest energy input. Notably, the CF bonds on the >CF₂ group are significantly weakened, with their bond dissociation energy lower than that of any CH bond in the molecule. In abstraction reactions, the reaction of F radical abstracting an H atom exhibits the lowest barrier; radical addition to the terminal carbon of the double bond is also more favorable. This work clarifies the oxidative decomposition process of 3,3,4,4,4-pentafluoro-1-butene, providing valuable support for assessing its thermal stability and flammability.

作为一种低全球变暖潜值的氢氟烯烃，3,3,4,4,4-五氟-1-丁烯含有一个双键，这引起了人们对其热稳定性的担忧，从而限制了其在制冷中的实际应用。本研究采用密度泛函理论研究其氧化分解机理，共探索了50种反应途径。这些结果表明，在初始热分解过程中，-CF₃基团的末端CC键最容易裂解，而末端CF键需要最高的能量输入。值得注意的是，>；CF₂基团上的CF键明显减弱，其键解离能低于分子中任何CH键。在抽离反应中，F自由基抽离H原子的能垒最低；双键末端碳的自由基加成也更有利。本研究阐明了3,3,4,4,4-五氟-1-丁烯的氧化分解过程，为评价其热稳定性和可燃性提供了有价值的支持。

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引用次数: 0

DFT mechanistic investigation of the cooperative N-heterocyclic carbene and photoinduced palladium catalysis in the regioselective alkylacylation of 1,3-dienes n -杂环羰基协同光诱导钯催化1,3-二烯区域选择性烷基酰化的DFT机理研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-01-10 DOI: 10.1016/j.comptc.2026.115673

Suravi Das, Sanchari Mukherjee, Gourab Kanti Das

A comprehensive DFT investigation was conducted to elucidate the mechanistic features of the cooperative NHC/Pd–photoredox catalytic system. Details of the energy profiles, NBO analysis, and spin-density calculations reveal the origins of the observed 1,2- versus 1,4-regioselectivity, showing that spin delocalisation, electronic effect, and steric effects jointly control the radical coupling step. Energetic evaluation confirms why the Pd-centred radical does not collapse with the allyl radical system toform Pd-allyl complexes. TD-DFT calculations show the singlet–triplet excitation and the wavelength required for generating the excited Pd species, and redox-potential (E°) values establish that the subsequent SET process is energetically accessible. The comparative study of two NHC systems reveals a distinct electronic nature that influences the stability of intermediates and catalyst turnover. Overall, this combined computational approach provides a coherent mechanistic analysis for radical formation, regioselectivity, and catalytic efficiency in NHC/Pd photoredox transformations.

通过DFT研究阐明了NHC/ pd -光氧化还原协同催化体系的机理特征。能量分布、NBO分析和自旋密度计算的细节揭示了观察到的1,2-和1,4-区域选择性的起源，表明自旋离域、电子效应和空间效应共同控制了自由基耦合步骤。能量评价证实了为什么以pd为中心的自由基不会与烯丙基自由基系统一起坍塌形成pd -烯丙基复合物。TD-DFT计算表明，单重态-三重态激发和产生激发态Pd所需的波长，氧化还原电位（E°）值确定了随后的SET过程在能量上是可访问的。两种NHC体系的比较研究揭示了影响中间体稳定性和催化剂周转的独特电子性质。总的来说，这种综合计算方法为NHC/Pd光氧化还原转化中的自由基形成、区域选择性和催化效率提供了连贯的机制分析。

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引用次数: 0

Research on the performance optimization of Y2Te3 thermoelectric materials based on strain engineering 基于应变工程的Y2Te3热电材料性能优化研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-01-10 DOI: 10.1016/j.comptc.2026.115677

Xinyue Zhang , Zhenqing Yang , Wansong Zhang, Changjin Shao, Yuhong Xia, Haoru Zhang, Chundan Lin

Advanced thermoelectric materials play a pivotal role in waste heat recovery. In this study, we systematically investigated the thermoelectric regulation mechanism of rare-earth chalcogenide Y₂Te₃ under axial strain using first-principles calculations combined with semi-classical Boltzmann transport theory. Our results demonstrate that at room temperature (300K), Y₂Te₃ exhibits superior thermoelectric performance along the c-axis. After strain optimization, the maximum power factors for p-type and n-type Y₂Te₃ reach 1.4 mW·m⁻¹·K⁻² and 14 mW·m⁻¹·K⁻², respectively, while the thermoelectric figure of merit (ZT) increases to 0.17 and 1.05, respectively. Benefiting from its inherently low lattice thermal conductivity, the ZT values of p-type and n-type Y₂Te₃ further increase to 0.52 and 2.1 at 800 K, respectively. This study not only highlights the outstanding thermoelectric properties of Y₂Te₃ but also underscores the substantial enhancement achieved through strain engineering, offering novel insights and theoretical support for the thermoelectric applications of rare-earth chalcogenides.

先进的热电材料在废热回收中起着举足轻重的作用。本文采用第一原理计算方法，结合半经典玻尔兹曼输运理论，系统地研究了稀土硫系化合物Y2Te3在轴向应变下的热电调控机理。我们的研究结果表明，在室温（300K）下，Y2Te3沿c轴表现出优越的热电性能。经过应变优化后，p型Y2Te3和n型Y2Te3的最大功率因子分别达到1.4 mW·m−1·K−2和14 mW·m−1·K−2，热电性能值（ZT）分别提高到0.17和1.05。由于其固有的低晶格导热系数，p型和n型Y2Te3的ZT值在800 K时分别增加到0.52和2.1。本研究不仅突出了Y2Te3优异的热电性能，而且强调了通过应变工程实现的实质性增强，为稀土硫族化合物的热电应用提供了新的见解和理论支持。

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引用次数: 0

Theoretical analysis of the electronic and supramolecular structure of 1,3-disubstituted 2-amino-1,3-benzimidazol-2-iminium iodides 1,3-二取代2-氨基-1,3-苯并咪唑-2-碘胺的电子结构和超分子结构的理论分析

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-01-08 DOI: 10.1016/j.comptc.2026.115662

Nina N. Chipanina, Bagrat А. Shainyan, Larisa V. Zhilitskaya, Nina O. Yarosh

The electronic and supramolecular structure of 1,3-bis-acylmethylated 1,3-dihydro-2H-benzo[d]imidazol-2-iminium iodide salts 1–3 was studied by the comparison of the X-ray data with DFT calculations of the monomeric salts and their dimers in gas and in polar medium. The layer structure of salt 1 in the crystal is determined not only by π-π stacking between the benzimidazole fragments, as asserted earlier, but also by the formation of two types of dimers, 1-D1 and 1-D2. In the former, the monomeric molecules are assembled via NH₂⋯I hydrogen bonds, whereas in dimer 1-D2 the NH₂⋯I and CH₂⋯I bonds belong to the same monomer. Dimer 1-D2 is much higher in energy being assembled by weak H-bonds of the carbonyl oxygen with the closest aromatic and aliphatic hydrogen atoms. For salts 1–3, the NBO and MESP analyses have been performed. A conclusion is made that the hydrogen bonding in salts may differ from that in non-ionic species.

通过x射线数据与气体和极性介质中单体盐及其二聚体的DFT计算结果的比较，研究了1,3-二酰基甲基化1,3-二氢- 2h -苯并咪唑-2-碘化亚胺盐1 - 3的电子结构和超分子结构。晶体中盐1的层状结构不仅是由先前断言的苯并咪唑片段之间的π-π堆积决定的，而且是由两种类型的二聚体1- d1和1- d2的形成决定的。在前者中，单体分子通过NH2⋯I氢键组装，而在二聚体1-D2中，NH2⋯I和CH2⋯I键属于同一单体。二聚体1-D2的能量要高得多，它是由羰基氧与最接近的芳香族和脂肪族氢原子形成的弱氢键组装而成的。对于盐1-3，进行了NBO和MESP分析。得出结论：盐类中的氢键可能与非离子型盐类中的氢键不同。

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引用次数: 0