Computational and Theoretical Chemistry最新文献_第9页

Atomic radial correlation energy density components 原子径向相关能量密度分量

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-14 DOI: 10.1016/j.comptc.2025.115597

Ibrahim E. Awad , Abd Al-Aziz A. Abu-Saleh , Gurleen Cheema , Joshua W. Hollett , Raymond A. Poirier

The components of the radial correlation energy density are calculated and analyzed for the atoms from He to Ar. The components include the nucleus-electron potential correlation energy density, the kinetic correlation energy density and the electron–electron potential correlation energy density. The necessary correlated one and two-electron density matrices are obtained from the Extrapolated-Full-Configuration-Interaction (exFCI) wave function where the reference wave function is restricted Hartree–Fock (RHF) or restricted open-shell Hartree–Fock (ROHF) depending on whether the atom is closed or open-shell. The accuracy associated with integrating the HF and exFCI energy density components, and the correlation energy density components, is evaluated on the SG-1 and SG-2 atomic grids. The SG-1 grid provides atomic energies that are accurate to about 1 kJ mol⁻¹, with the exception of the kinetic energy. The SG-2 grid is required for the analysis of atomic kinetic energies and more subtle energetic effects. There is also a significant amount of integration error cancellation in the correlation energy densities. The radial correlation energy densities display notable shell structure, and there is a substantial difference between the

α

and

β

-electron correlation energy densities for the open-shell atoms.

计算并分析了He - Ar原子径向相关能密度的组成，包括核-电子势相关能密度、动力学相关能密度和电子-电子势相关能密度。从外推全构型相互作用（exFCI）波函数中得到必要的相关单电子和双电子密度矩阵，其中参考波函数是受限Hartree-Fock （RHF）或受限开壳Hartree-Fock (ROHF)，取决于原子是闭合还是开壳。在SG-1和SG-2原子网格上对HF和exFCI能量密度分量以及相关能量密度分量的积分精度进行了评估。SG-1网格提供的原子能量精确到1 kJ mol−1左右，动能除外。SG-2网格是分析原子动能和更微妙的能量效应所必需的。在相关能量密度中也有大量的积分误差抵消。径向相关能密度表现出明显的壳层结构，开壳原子的α -电子相关能密度与β-电子相关能密度存在较大差异。

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引用次数: 0

Study on water-acid synergistic effects in the diffusion of natural ester-mineral oil blends by molecular dynamics simulation 用分子动力学模拟研究天然酯-矿物油共混物在扩散过程中的水-酸协同效应

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-14 DOI: 10.1016/j.comptc.2025.115595

Yujing Tang, Yanan Tang, Lei Zhang, Qiang Ou, Qi Wang

The moisture and small acid in insulation oil accelerate the aging of transformer oil paper insulation, which seriously threatens the safe operation of the transformer. In this work, the diffusion mechanism of natural ester oil-paper interface model (zwy), mineral oil-paper interface model (kwy) and natural ester blend mineral oil-paper interface model (hhy) under the synergistic action of water and formic acid were studied by molecular dynamics. The mean square displacement, radial distribution function, interaction energy, free volume and hydrogen bond were analyzed. The results show that the diffusion rates for water and formic acid are between 4.8 and 7.3 times greater in the hhy system blend compared to zwy system. When compared to the kwy system, the diffusion rates in the hhy are 0.7 and 1.2 times. Meanwhile, compared to kwy and hhy, zwy is more likely to form hydrogen bonding networks. At the same time, the movement of water molecules and formic acid in zwy was restricted, and the free volume fraction was relatively low. When the temperature rises from 298 K to 393 K, the breaking rates of kwy, zwy, and hhy hydrogen bonds were 4.7 %, 5.6 %, and 3.2 %, respectively. The results provide a theoretical basis and microscopic mechanism for the diffusion mechanism of water and small acid molecules in oil paper insulation systems.

绝缘油中的水分和小酸加速了变压器油纸绝缘的老化，严重威胁到变压器的安全运行。本文采用分子动力学方法研究了天然酯油纸界面模型（zwy）、矿物油纸界面模型（kwy）和天然酯混合矿物油纸界面模型（hhy）在水和甲酸协同作用下的扩散机理。分析了均方位移、径向分布函数、相互作用能、自由体积和氢键。结果表明，在hhy体系中，水和甲酸的扩散速率是zwy体系的4.8 ~ 7.3倍。hhy体系的扩散速率是kwy体系的0.7倍和1.2倍。同时，与kwy和hhy相比，zwy更容易形成氢键网络。同时，水分子和甲酸在zwy中的运动受到限制，自由体积分数相对较低。当温度从298 K升高到393 K时，kwy、zwy和hhy氢键断裂率分别为4.7%、5.6%和3.2%。研究结果为油纸绝缘体系中水和酸小分子的扩散机理提供了理论依据和微观机理。

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引用次数: 0

Rational design and excited-state properties study of efficient hot exciton luminescent materials 高效热激子发光材料的合理设计与激发态特性研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-12 DOI: 10.1016/j.comptc.2025.115593

Peng-Yuan Li , Fu-Quan Bai

Conventional TADF materials face a fundamental trade-off between small S₁-T₁ energy gap and fast S₁ radiative decay due to S₁'s dual role in RISC and emission. To address this conflict, we theoretically designed a series of novel ‘donor-anthracene-acceptor’ molecules via excited-state kinetics regulation and multi-parameter optimization. All molecules exhibit distinct T₂ excitation channels, decoupling T₂ → S₁ RISC from S₁ → S₀ emission. This strategy holds the potential for independent control of exciton utilization and luminescence intensity. DFT calculations reveal how the anthracene-donor/acceptor dihedral angle critically influences S₁-T₂ SOC, revealing a structure-property relationship for SOC tuning. Our calculations predict that the optimized candidate C4 would significantly suppress T₂ → T₁ internal conversion, with a predicted T₂ lifetime of 183 ns that could facilitate efficient spin-flip. This work proposes promising theoretical candidates for efficient hot exciton emitters and provides a computational framework for guiding the precise control of exciton kinetics via systematic excited-state analysis.

由于S1在RISC和发射中的双重作用，传统的TADF材料面临着S1- t1小能隙和快速S1辐射衰减之间的基本权衡。为了解决这一矛盾，我们通过激发态动力学调节和多参数优化，从理论上设计了一系列新的“供体-蒽-受体”分子。所有分子都表现出不同的T2激发通道，将T2→S1的RISC与S1→S0的发射解耦。这种策略具有独立控制激子利用和发光强度的潜力。DFT计算揭示了蒽-给体/受体二面角如何严重影响S1-T2荷电性，揭示了荷电性调谐的结构-性质关系。我们的计算预测优化后的候选C4将显著抑制T2→T1的内部转换，预计T2寿命为183 ns，可以促进有效的自旋翻转。这项工作提出了有效的热激子发射的有前途的理论候选人，并提供了一个计算框架，指导激子动力学的精确控制，通过系统的激发态分析。

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引用次数: 0

Exploring self-aggregation and microhydration in diversified three-membered heterocycles: 2H-Azirine 探索多元三元杂环：2H-Azirine的自聚集和微水化

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-11 DOI: 10.1016/j.comptc.2025.115591

Dipali N. Lande , Shridhar P. Gejji , Rajeev K. Pathak

Azirine, a highly strained three-membered heterocyclic imine, is speculated to occur in the interstellar medium (ISM). The present study purports that the stable 2H-Azirine that supersedes (by ∼138 kJ⋅mol⁻¹ in binding energy) over its 1H-isomer, evokes strong self-aggregation and limited ‘microhydration’ through cooperative hydrogen bonding, a propensity that it shares with cyclopropenylidene and other related heterocyclic systems. We employ the ωB97xD/6–311++G(2d,2p) density functional theory (DFT) to derive cluster binding energies, molecular electrostatic potential (MESP) maps, effective atomic charges, infrared spectroscopic responses, tenets of criticality ensuing from the quantum theory of atoms in molecules (QTAIM), hydrogen-bond energies, and reduced density gradient (RDG) portrayals that elicit the underlying noncovalent interactions (NCI), depicting their diverse patterns in real space. All these molecular descriptors that concur on cooperativity, yield energies that scale linearly from the dimer through octamer, each monomer adding ∼21 kJ⋅mol⁻¹ on an average. With incremental aggregation, vibrational frequencies reveal nominal down-shifts of about 7–9 cm⁻¹ for C=N stretching; while in microhydrated 2H-Azirine, O-H vibrations display a major down-shift of ∼369 cm⁻¹. The present study should bolster identification of 2H-Azirine in the ISM either in its pristine form, or its aggregated / microhydrated configurations.

Azirine是一种高度应变的三元杂环亚胺，推测存在于星际介质（ISM）中。目前的研究表明，稳定的2H-Azirine取代了其1h -异构体（结合能约138 kJ·mol−1），通过合作氢键引起了强烈的自聚集和有限的“微水化”，它与环丙烯和其他相关的杂环系统具有相同的倾向。我们采用ωB97xD/ 6-311 ++G（2d,2p）密度泛函理论（DFT）推导出团簇结合能、分子静电势（MESP）图、有效原子电荷、红外光谱响应、分子原子量子理论（QTAIM）得出的临界原理、氢键能和减少密度梯度（RDG）描述，这些描述引发了潜在的非共价相互作用（NCI），描绘了它们在实际空间中的不同模式。所有这些协同性一致的分子描述符，产生的能量从二聚体到八聚体呈线性增长，每个单体平均增加约21 kJ·mol−1。随着聚集的增加，C=N拉伸的振动频率显示出约7-9 cm−1的标称下降；而在微水合2H-Azirine中，O-H振动显示出~ 369 cm−1的主要下移。本研究应加强对ISM中2H-Azirine的识别，无论是其原始形式，还是其聚集/微水合构型。

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引用次数: 0

Unveiling the sensing mechanism of Ti2Pc and V2Pc monolayers for volatile organic compounds detection: A first-principles perspective 揭示Ti2Pc和V2Pc单层对挥发性有机化合物检测的传感机制：第一性原理视角

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-11 DOI: 10.1016/j.comptc.2025.115589

Shulin Zhang , Hailong Xi , Xiaojian Ou , Yongfeng Ma , Caifang Cao , Huihui Xiong

Volatile organic compounds (VOCs) constitute pivotal precursors to ozone and PM2.5 pollution, and can also directly irritate the human body, triggering a variety of diseases. Consequently, the development of VOCs sensors with exceptional sensitivity and robust stability represents a critical imperative for environmental monitoring. Herein, the adsorption behavior and gas-sensing performance of bimetallic phthalocyanines M₂Pc (Ti₂Pc and V₂Pc) toward five representative VOCs (H₂CO, C₂H₄, C₆H₆, CH₃Cl and CH₃OH) were systematically investigated using first-principles calculations, with comprehensive analysis of the electronic properties for each adsorption system. The results show that both Ti₂Pc and V₂Pc monolayers exhibit excellent structural stability and strong chemisorption toward all five VOC molecules. The pronounced interactions between M₂Pc and VOCs are systematically elucidated through analyses of differential charge density, charge transfer, and density of states. Notably, the adsorption of C₂H₄ and C₆H₆ leads to the quenching of the magnetic moment in V₂Pc monolayers, while the adsorption of CH₃Cl and CH₃OH induces a semiconductor-to-metal transition in V₂Pc. Variations in band gap, work function, and magnetic moment before and after gas adsorption reveal the distinct sensitivity of Ti₂Pc and V₂Pc monolayers to different VOCs. Finally, recovery time analysis indicates that both Ti₂Pc and V₂Pc monolayers are highly promising as reusable CH₃Cl gas sensors. These findings provide a solid theoretical foundation for the development and fabrication of high-performance bimetallic phthalocyanine-based gas sensors.

挥发性有机化合物（VOCs）是臭氧和PM2.5污染的关键前体，也会直接刺激人体，引发多种疾病。因此，开发具有卓越灵敏度和强大稳定性的VOCs传感器对于环境监测至关重要。本文采用第一性原理计算方法，系统研究了双金属酞菁M2Pc （Ti2Pc和V2Pc）对5种代表性VOCs （H2CO、C2H4、C6H6、CH3Cl和CH3OH）的吸附行为和气敏性能，并对各吸附体系的电子性质进行了综合分析。结果表明，Ti2Pc和V2Pc单层膜对5种VOC分子均表现出良好的结构稳定性和较强的化学吸附性。通过电荷密度、电荷转移和态密度的分析，系统地阐明了M2Pc与VOCs之间明显的相互作用。值得注意的是，C2H4和C6H6的吸附导致了V2Pc单层中磁矩的猝灭，而CH3Cl和CH3OH的吸附则导致了V2Pc中半导体到金属的转变。气体吸附前后带隙、功函数和磁矩的变化揭示了Ti2Pc和V2Pc单层膜对不同VOCs的不同敏感性。最后，回收时间分析表明，Ti2Pc和V2Pc单层膜都是非常有前途的可重复使用的CH3Cl气体传感器。这些发现为开发和制造高性能双金属酞菁气体传感器提供了坚实的理论基础。

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引用次数: 0

Structural, electronic, and magnetic properties of CrMnPbn (n = 3–20) clusters CrMnPbn （n = 3-20）簇的结构、电子和磁性能

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-10 DOI: 10.1016/j.comptc.2025.115588

Gen Liu , Zejin Wu , Zhouhe Yang , Hongwei Wang , Kai Wang

A deep understanding of magnetic clusters is fundamental to connecting atomic and bulk magnetism, which supplies new pathways for designing next-generation nanomaterials. Herein, the structures, and electronic and magnetic properties of CrMnPb_n (n = 3–20) clusters are systematically investigated using a global optimization algorithm coupled with density functional theory (DFT). The results reveal that Cr and Mn atoms consistently form a direct bond and become progressively encapsulated with increasing Pb atoms, leading to endohedral configurations. The CrMnPb_n clusters, similar to Cr₂Sn_n and Cr₂Pb_n clusters, show a preference for icosahedral and douible-icosahedral geometries, distinct from the hexagonal prism, hexagonal anti-prism, or fullerene-like structures often found in Si/Ge-based analogues. All CrMnPb_n clusters consistently display antiferromagnetic (AFM) coupling between Cr and Mn atoms through their opposite magnetic moments. Furthermore, the geometric and magnetic properties of the CrMnPb₁₇ monomer remain robust upon dimerization, underscoring its potential as a promising building block for AFM nanoscale assemblies.

对磁性团簇的深入理解是连接原子磁性和体磁性的基础，为设计下一代纳米材料提供了新的途径。本文采用密度泛函理论（DFT）结合全局优化算法，系统地研究了CrMnPbn （n = 3-20）簇的结构、电子和磁性能。结果表明，Cr和Mn原子一致形成直接键，并逐渐被Pb原子包裹，形成内嵌结构。CrMnPbn簇簇与Cr2Snn和Cr2Pbn簇簇类似，表现出对二十面体和双二十面体的偏好，不同于Si/ ge基类似物中常见的六角形棱镜、六角形反棱镜或类富勒烯结构。所有的CrMnPbn簇通过相反的磁矩在Cr和Mn原子之间一致地表现出反铁磁耦合（AFM）。此外，在二聚化过程中，CrMnPb17单体的几何和磁性仍然保持稳定，这表明它有潜力成为AFM纳米级组件的有前途的构建块。

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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 : 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

A computational approach to understand stepwise PCET during hydrogen evolution reaction by iron dithiolene catalyst 二硫代铁催化析氢反应中PCET的计算方法

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-06 DOI: 10.1016/j.comptc.2025.115564

Koushik Makhal , Bhabani S. Mallik

We examined the mechanistic insights into hydrogenation and dehydrogenation reactions, encompassing various conceivable pathways of two-electron and two-proton addition reactions catalyzed by redox Fe dithiolene complexes using computational methods. The investigation considers both ligand-mediated and ligand-metal-mediated reaction paths. The plausible pathway for adding two protons and two electrons is the ECEC (E electron transfer process, C proton transfer process) sequence involving protonation at the Fe center and one S center. A decrease in the spin density at the metal center during FeH bond formation is indicative of electron transfer from the Fe to the hydrogen and sulfur centers. The d orbital of the Fe center is engaged with the s orbital of a hydrogen atom. But the p_y orbital of the sulfur atom interacts with the s orbital of hydrogen, culminating in the formation of an SH bond. In the dehydrogenation reaction, H₂ formation occurs at the FeH and SH sites.

我们研究了加氢和脱氢反应的机理，包括由氧化还原铁二硫烯配合物催化的各种可能的双电子和双质子加成反应途径。该研究考虑了配体介导和配体-金属介导的反应途径。加入两个质子和两个电子的可能途径是ECEC （E电子转移过程，C质子转移过程）序列，包括Fe中心和一个S中心的质子化。在FeH键形成过程中，金属中心自旋密度的降低表明电子从Fe转移到氢和硫中心。铁中心的d轨道与氢原子的s轨道相连。但是硫原子的py轨道与氢的s轨道相互作用，最终形成SH键。在脱氢反应中，H2生成发生在FeH和SH位点。

引用次数: 0

First-principles study of Ni/Cu doped Janus ZrSSe monolayers for selective and high-affinity sensing of industrial pollutant gases Ni/Cu掺杂Janus ZrSSe单层膜对工业污染气体选择性和高亲和感测的第一性原理研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-05 DOI: 10.1016/j.comptc.2025.115585

Zinah H. Obaid, Lafy F. Al-Badry

In this study, the toxic gases such as NO₂, SO₂, CO₂, and CO contribute to air pollution, making their detection essential for environmental monitoring and public safety. The gas adsorption behavior of NO₂, SO₂, CO₂, and CO molecules on Ni- and Cu-doped Janus ZrSSe monolayers was systematically investigated using first-principles computations based on density functional theory (DFT). The results reveal that NO₂ exhibits the strongest interaction with both doped surfaces, possessing the most significant recorded adsorption energy for Ni-doped ZrSSe (−4.28 eV), followed by Cu-doped ZrSSe (−3.71 eV). The large difference between the band gaps before and after adsorption certainly generates a high sensitivity to NO₂ gas in the Ni-ZrSSe system, which reaches 119.09. These results highlight the potential of Ni-ZrSSe, in particular, as a promising applicant for NO₂ gas sensing applications due to its enhanced adsorption capability.

在本研究中，NO2、SO2、CO2、CO等有毒气体是造成大气污染的主要原因，因此对这些有毒气体的检测对于环境监测和公共安全至关重要。采用基于密度泛函理论（DFT）的第一性原理计算方法，系统地研究了NO2、SO2、CO2和CO分子在Ni和cu掺杂Janus ZrSSe单层上的气体吸附行为。结果表明，NO2与两种掺杂表面的相互作用最强，对ni掺杂ZrSSe具有最大的吸附能（- 4.28 eV），其次是cu掺杂ZrSSe （- 3.71 eV）。吸附前后带隙的较大差异必然导致Ni-ZrSSe体系对NO2气体的灵敏度较高，达到119.09。这些结果突出了Ni-ZrSSe的潜力，特别是由于其增强的吸附能力，它在NO₂气体传感应用中具有很好的应用前景。

引用次数: 0

Coupling DFT with PCA for a comprehensive study of Rb-based 5d transition metal hydride perovskites for hydrogen storage applications 耦合DFT与PCA对rb基5d过渡金属氢化物钙钛矿储氢应用的综合研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-11-05 DOI: 10.1016/j.comptc.2025.115586

Mohamed Boubchir , Rachid Boubchir , Nadir Mohamed Belmessaoud , Merzoug Kadous , Hafid Aourag , Bachir Bouhafs

In this study, a systematic first-principles investigation of a newly discovered hydride perovskite compound is presented by density functional theory (DFT). The investigation covers the structural, electronic, magnetic, and the phonon properties as a means of evaluating the stability as well as the functionality of the compound. The optimised crystal structure confirms the thermodynamic stability of the compound, and the calculated lattice constants agree well with the expected perovskite symmetry. Electronic band structure as well as density of states (DOS) calculations confirm a half metallic character, which highlights the effect of hydrogen incorporation on electronic behavior. Further, the calculations of the phonon dispersions prove the absence of imaginary frequencies across the Brillouin zone, and thus confirming the dynamic stability of the hydride perovskite, which exhibits profound gravimetric H₂ storing capacities. The Rb-Based 5d Transition Metal exhibits gravimetric H₂ storing densities of 1.133 wt%, 1.121 wt%, as well as 1.111 wt% for (Ta, W, and Re), respectively. The results reported in this work reveal that this family of hydrogen-rich perovskites offers a potential use as a technology for storing hydrogen as well as for other energy-related purposes.

本文利用密度泛函理论（DFT）对一种新发现的氢化物钙钛矿化合物进行了系统的第一性原理研究。该研究涵盖了结构、电子、磁性和声子性质，作为评估化合物稳定性和功能的手段。优化后的晶体结构证实了化合物的热力学稳定性，计算出的晶格常数与预期的钙钛矿对称性很好地吻合。电子能带结构和态密度（DOS）计算证实了半金属性质，这突出了氢掺入对电子行为的影响。此外，声子色散的计算证明了在布里渊区不存在虚频率，从而证实了氢化物钙钛矿的动态稳定性，它具有深刻的重力储氢能力。rb基5d过渡金属（Ta、W和Re）的重量储氢密度分别为1.133 wt%、1.121 wt%和1.111 wt%。这项工作报告的结果表明，这种富氢钙钛矿家族提供了一种潜在的用途，作为一种储存氢的技术以及其他与能源相关的用途。

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引用次数: 0