Computational and Theoretical Chemistry最新文献_第2页

Hydrogen storage in second-row transition metal-decorated phosphorene nanoflakes: A DFT investigation 第二行过渡金属修饰磷烯纳米片中的储氢：DFT研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2026-01-01 DOI: 10.1016/j.comptc.2025.115656

Cesar Gabriel Vera de la Garza, Wilmer Esteban Vallejo Narvaez. Serguei Fomine

The hydrogen storage capacity of second-row transition-metal-decorated phosphorene nanoflakes (NFs) was investigated theoretically using the wB97M-D4/def2-TZVP(−f) level of theory. All second-row transition metals were found to form stable complexes with the phosphorene NFs. Among the series, NFs decorated with Mo, W, and Nb formed exergonic complexes with molecular hydrogen, with each metal atom capable of binding up to three H₂ molecules. The calculated Gibbs free binding energies ranged from −24.34 kcal/mol for the P–W–H₂ complex to 22.94 kcal/mol for the P–Y–H₂ complex. These complexes form without a significant activation energy barrier and involve partial dissociation of the HH bond. In specific cases, such as with W, Nb, and Mo, the binding mechanism involves hydride formation. Ab initio molecular dynamics simulations revealed a dynamic equilibrium between physisorption and chemisorption of H₂ molecules. The theoretical highest hydrogen storage capacities, approximately 2.73–2.77 wt%, were exhibited by Mo, W, and Nb.

采用wB97M-D4/def2-TZVP（−f）理论研究了第二行过渡金属修饰磷烯纳米片（NFs）的储氢能力。所有第二行过渡金属均与磷烯形成稳定的配合物。在这一系列中，以Mo、W和Nb修饰的NFs与分子氢形成了助能配合物，每个金属原子能够结合多达3个H₂分子。计算得到的吉布斯自由结合能从P-W-H2络合物的−24.34 kcal/mol到P-Y-H2络合物的22.94 kcal/mol不等。这些配合物的形成没有明显的活化能屏障，并涉及HH键的部分解离。在特定情况下，如W、Nb和Mo，结合机制涉及氢化物的形成。从头算分子动力学模拟揭示了H2分子的物理吸附和化学吸附之间的动态平衡。Mo、W和Nb的理论储氢量最高，约为2.73-2.77 wt%。

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引用次数: 0

Photophysical properties of D-π-A-π-A organic dyes with benzodiazole-based auxiliary acceptors: A computational study 含苯二氮唑类辅助受体的D-π-A-π-A有机染料的光物理性质计算研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-31 DOI: 10.1016/j.comptc.2025.115655

Yun Wang, Hai-Bei Li

This computational study systematically investigates a series of D-π-A-π-A organic dyes featuring triphenylamine as the donor, cyanoacrylic acid as the acceptor, and benzodiazole-based auxiliary acceptors (A1) with varied bridging moieties (CH₂, NH, O, S, Se, and Te). Using density functional theory (DFT) and time-dependent DFT, we analyze their geometries, frontier orbitals, UV–Vis absorption, charge-transfer characteristics, and key photovoltaic parameters. All dyes exhibit favorable charge separation, suitable energy alignment with TiO₂ and electrolyte, high light-harvesting efficiency (>98 %), and sufficient open-circuit voltage (>0.7 V). Notably, the benzimidazole-based dye shows the smallest HOMO-LUMO gap and the most red-shifted absorption, highlighting its superior potential as a sensitizer. The work establishes a clear structure-property relationship and provides valuable insights for tailoring auxiliary acceptors for designing high-performance organic dyes.

本计算研究系统地研究了一系列以三苯胺为供体，氰丙烯酸为受体，以不同桥接基团（CH2， NH， O， S， Se和Te）为辅助受体（A1）的D-π-A-π-A有机染料。利用密度泛函理论（DFT）和时变DFT分析了它们的几何形状、前沿轨道、紫外-可见吸收、电荷转移特性和关键光伏参数。所有染料均表现出良好的电荷分离性、与tio2和电解质的能量匹配、高的光收集效率（> 98%）和足够的开路电压（>0.7 V）。值得注意的是，苯并咪唑基染料显示出最小的HOMO-LUMO间隙和最多的红移吸收，突出了其作为敏化剂的优越潜力。这项工作建立了清晰的结构-性能关系，为设计高性能有机染料的辅助受体提供了有价值的见解。

引用次数: 0

Temperature-dependent decomposition mechanism of a hot DNP/DNTF liquid eutectic model: Molecular-level insights from SCC-DFTB calculations 热DNP/DNTF液体共晶模型的温度依赖分解机制：来自SCC-DFTB计算的分子水平见解

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-30 DOI: 10.1016/j.comptc.2025.115650

Yahong Chen , Zixuan Yang , Fangfang Hou , Shuangfei Zhu , Ruijun Gou , Shuhai Zhang

Self-consistent charge density functional tight-binding (SCC-DFTB) molecular dynamics simulations were employed to study the initial thermal decomposition mechanisms of 3,4-dinitro-1H-pyrazole (DNP) and 3,4-dinitrofurazanfuroxan (DNTF) eutectic mixture. Different from ordered and disordered models, the eutectic system exhibits unique decomposition behaviors. NO bond cleavage of DNTF predominates and increases with temperature, followed mainly by furoxan ring opening via CC breakage. NN bond rupture of DNP prevails, and pyrazole ring opening shifts to NN bong cleavage. Notably, DNTF decomposes more readily, while DNP reactivity lies intermediately. The eutetic system also exhibited significantly distinct decomposition product characteristics compared to both ordered and disordered models. The typical cleavage products of DNP and DNTF in the eutetic model were analyzed to revealed the thermal decomposition mechanism under different molecular stacking patterns. These results elucidate the synergy between molecular packing and temperature in governing decomposition mechanisms, advancing the understanding of sensitivity and thermal behavior in energetic materials.

采用自一致电荷密度功能紧密结合（SCC-DFTB）分子动力学模拟研究了3,4-二硝基- 1h -吡唑（DNP）和3,4-二硝基呋喃呋喃（DNTF）共晶混合物的初始热分解机理。与有序模型和无序模型不同，共晶体系表现出独特的分解行为。DNTF的NO键断裂为主，并随温度升高而增加，其次是呋喃酮环通过CC断裂打开。DNP以NN键断裂为主，吡唑环开口向NN键解理转变。值得注意的是，DNTF更容易分解，而DNP的反应性处于中间状态。与有序模型和无序模型相比，共晶体系也表现出明显不同的分解产物特征。分析了DNP和DNTF在共晶模型中的典型裂解产物，揭示了不同分子堆积模式下的热分解机理。这些结果阐明了分子堆积和温度在控制分解机制中的协同作用，促进了对含能材料的灵敏度和热行为的理解。

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引用次数: 0

New mechanistic pathways for the reactions of glyoxal with sulfuric acid and formic acid in atmosphere: The initial process of atmospheric nucleation 乙二醛与硫酸和甲酸在大气中反应的新机理途径：大气成核的初始过程

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-30 DOI: 10.1016/j.comptc.2025.115654

Jiyu Liu , Yongchao Zhao , Huafeng Wu , Meimei Yu , Zezhuan Jiang

Glyoxal (CHO)₂, an important oxidation product of volatile organic compounds (VOCs), acts as a key precursor to secondary organic aerosols (SOA), which influence atmospheric chemistry, cloud formation, and climate. Yet, its gas-phase reactions with small molecular acids and their catalytic roles in atmospheric nucleation remain unclear. Here, density functional theory (DFT) and high-level ab initio methods were used to explore the reaction pathways of glyoxal with sulfuric acid (H₂SO₄) and formic acid (HCOOH). Both acids exhibit strong catalytic effects, lowering activation barriers by 15.29 and 14.63 kcal·mol⁻¹, respectively. Kinetic analyses show that the (HCO)₂ + H₂SO₄ reaction is the fastest, producing H(CHO)₂OSO₃H, which contributes to gas-phase degradation of glyoxal and sulfuric acid. The resulting binary complex may serve as a new nucleation precursor, providing insight into the early stages of atmospheric nucleation and SOA formation.

乙二醛（CHO） 2是挥发性有机化合物（VOCs）的重要氧化产物，是二次有机气溶胶（SOA）的关键前体，影响大气化学、云的形成和气候。然而，其与小分子酸的气相反应及其在大气成核中的催化作用尚不清楚。本文采用密度泛函理论（DFT）和高阶从头算方法探讨了乙二醛与硫酸（H₂SO₄）和甲酸（HCOOH）的反应途径。两种酸均表现出较强的催化作用，分别降低了15.29和14.63 kcal·mol−1的活化势垒。动力学分析表明，（HCO）₂+ H₂SO₄反应速度最快，生成H（CHO）₂OSO₃H，有利于乙二醛和硫酸的气相降解。由此产生的二元配合物可以作为一种新的成核前体，为大气成核和SOA形成的早期阶段提供见解。

引用次数: 0

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 : 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

Tuning of π-spacer engineering in D–π–A organic dyes for dye-sensitized solar cells: DFT/TD-DFT insights into enhanced optoelectronic and charge-transport properties 用于染料敏化太阳能电池的D -π-A有机染料中π-间隔层工程的调谐：DFT/TD-DFT对增强光电和电荷输运性质的见解

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-29 DOI: 10.1016/j.comptc.2025.115643

Ananta Panigrahi, Prabhat K. Sahu

This study presents a series of novel D–π–A organic dyes (1 A–4H) designed for dye-sensitized solar cells (DSSCs) using DFT and TD-DFT at 6–31 + G* level. Incorporating donor groups (amino, dimethylamine, methoxy, diphenylamine), fused thiophene and Thiazolo[5,4-d] thiazole π-spacers, and acceptors like –NO₂, –CN, and cyanoacrylic acid (CAA), the dyes are analyzed for optoelectronic performance. CAA-based dyes show enhanced intramolecular charge transfer, red-shifted absorption, and higher molar extinction coefficients. Dyes 1F, 1H, 4F, and 4H exhibit broader absorption bands, higher light-harvesting efficiency (up to 96.17 %), lower chemical hardness, and stronger electron injection driving force. Their large vertical dipole moments and increased conduction band electron population support superior photovoltaic performance. The computed results also support with favourable ionization energy, electron affinity, and reorganization energies. These findings highlight 1F, 1H, 4F, and 4H dyes for high-efficiency DSSC applications, warranting further experimental validation.

本研究利用DFT和TD-DFT在6-31 + G*水平上设计了一系列用于染料敏化太阳能电池（DSSCs）的新型D -π-A有机染料（1 a - 4h）。结合给基（氨基、二甲胺、甲氧基、二苯胺）、融合噻吩和噻唑[5,4-d]噻唑π-间隔基团以及受体（-NO₂、-CN、氰丙烯酸（CAA）），对染料进行了光电性能分析。caa基染料表现出增强的分子内电荷转移、红移吸收和更高的摩尔消光系数。染料1F、1H、4F和4H具有较宽的吸收带、较高的光收集效率（可达96.17%）、较低的化学硬度和较强的电子注入驱动力。它们大的垂直偶极矩和增加的导带电子居群支持优越的光伏性能。计算结果也支持有利的电离能、电子亲和能和重组能。这些发现突出了1F、1H、4F和4H染料在高效DSSC中的应用，需要进一步的实验验证。

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引用次数: 0

CO oxidation on noble-metal-free niobium‑nickel monoxide anion under NO/CO Co-adsorption NO/CO共吸附下无贵金属铌镍阴离子上的CO氧化

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-29 DOI: 10.1016/j.comptc.2025.115651

Jumei Zhang , Ziheng Zhang , Menghan Zhao , Weiwei Chen , Jiao Wang , Jinghan Zou , Xiangtao Kong , Hua Xie , Hongjin Qiao

Carbon monoxide (CO) oxidation is pivotal for exhaust-gas purification. Ambient co-adsorbates nitrogen monoxide (NO) can significantly affect CO oxidation. Herein, a series of NbNiO(NO)(CO)_n⁻ (n = 1–6) clusters were investigated by density functional theory. A bridging-O structure is most favorable for n = 1–3, then a terminal-O structure becomes favored for n = 4–5, and finally a CO₂-tagged structure is most favorable for n = 6. NO preferentially adsorbs at niobium (Nb) site, promoting CO oxidation by mediating the NbO interactions. During the consecutive CO adsorption, NO acts as an electron donor, and the metal centers display complementary electron transfer behavior: Nb acts as an electron acceptor for n ≤ 3, then switches to an electron donor at n = 4–5, and finally acts as an electron acceptor at n = 6, whereas nickel (Ni) exhibits the opposite trend. These findings provide atomistic insights into CO oxidation over heteronuclear metal oxides under co-adsorption conditions.

一氧化碳（CO）氧化是废气净化的关键。环境共吸附一氧化氮（NO）对CO氧化有显著影响。本文利用密度泛函理论研究了一系列NbNiO(NO)(CO)n−(n = 1-6)簇。当n = 1-3时，桥接o型结构最有利，当n = 4-5时，末端o型结构最有利，当n = 6时，co2标记型结构最有利。NO优先吸附在铌（Nb）位点，通过介导NbO相互作用促进CO氧化。在连续CO吸附过程中，NO作为电子给体，金属中心表现出互补电子转移行为：Nb在n≤3时为电子受体，在n = 4-5时转变为电子给体，在n = 6时最终成为电子受体，而镍（Ni）则表现出相反的趋势。这些发现提供了CO在共吸附条件下在异核金属氧化物上氧化的原子性见解。

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引用次数: 0

Antiferromagnetic B₄C₄ superatomic monolayer acting as high-capacity calcium-ion battery anode 反铁磁B₄C₄超原子单层用作高容量钙离子电池负极

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-29 DOI: 10.1016/j.comptc.2025.115647

Huan Yuan , Kaidong Shen , Chang Xu , Qiquan Luo

Calcium-ion batteries (CIBs) represent a promising next-generation energy storage technology due to earth-abundant of calcium element and high theoretical energy density. However, the application of CIBs is still hindered by the lack of high-performance anode materials, particularly those suffering from limited storage capacity and sluggish diffusion kinetics induced by large ionic radius of Ca ion. To address this challenge, this paper proposes a porous superatom-assembled B₄C₄ monolayer from first principles calculation, as a promising anode candidate for CIBs. Electronic analysis confirms the 14e superatomic shell of B₄C₂ building block, which linked by two edge carbon atoms with unpaired electrons resulting in an antiferromagnetic ground state. This electronic configuration significantly enhances the material's affinity for Ca, due to the formation of multi-center bonding between Ca and single-occupied C atoms. Remarkably, the B₄C₄ anode delivers an ultrahigh theoretical capacity of 3495.80 mAh g⁻¹, with a low Ca ion diffusion barrier of 0.59 eV, facilitating rapid charge/discharge rates. The average open-circuit voltage is decrease gradually from 0.94 V to 0.20 V with increasing Ca concentration. This work not only predicts a promising anode candidate for CIBs, but also establishes antiferromagnetic materials with unpair electron as a new paradigm for advanced battery design.

钙离子电池具有丰富的钙元素和较高的理论能量密度，是一种很有前途的下一代储能技术。然而，高性能阳极材料的缺乏仍然阻碍了cib的应用，特别是由于Ca离子的大离子半径导致的存储容量有限和扩散动力学缓慢。为了解决这一挑战，本文从第一性原理计算中提出了一种多孔超原子组装的B₄C₄单层，作为cib的有希望的阳极候选材料。电子分析证实了B₄C2构建块的14e超原子壳层，它由两个边缘碳原子与不成对电子连接，导致反铁磁基态。由于Ca和单占据的C原子之间形成了多中心键，这种电子构型显著增强了材料对Ca的亲和力。值得注意的是，B₄C₄阳极提供了3495.80 mAh g−1的超高理论容量，具有0.59 eV的低Ca离子扩散势垒，有利于快速充放电。随着Ca浓度的增加，平均开路电压从0.94 V逐渐降低到0.20 V。这项工作不仅预测了一种有希望的cib阳极候选材料，而且为先进电池设计建立了一种具有解对电子的反铁磁性材料。

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引用次数: 0

Computational study of phosphorus-bearing molecule adsorption on amorphous silica: energetics and infrared signatures with relevance for interstellar and terrestrial chemistry 含磷分子在无定形二氧化硅上吸附的计算研究：与星际和地球化学相关的能量学和红外特征

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-29 DOI: 10.1016/j.comptc.2025.115652

Mireille Amandjigbeto , Etienne P. Hessou , Gaston Kpotin , Yacolé G.S. Atohoun , Ionut Tranca , Vicente Timon , Frederik Tielens

The adsorption behaviour of five phosphorus-bearing molecules (PO, PO₂, POH, HPO and PH₃) on amorphous silica, as a representative model not only for interstellar silicate dust grains but also for terrestrial silicate surfaces that play a role in prebiotic and geochemical processes, has been investigated to elucidate their sorption and spectroscopic characteristics. The dispersion-corrected density functional theory (DFT-D3) within the VASP framework was employed. The calculated adsorption energies are all negative, indicating that the adsorption processes are exothermic and thermodynamically favorable. Intermolecular distances and Bader charges confirm chemisorption as the dominant interaction mode, consistent with the observed energetics. Infrared (IR) spectra further demonstrate the formation of chemical bonds between the adsorbed species and the silica surface. While the spectra of PO and PO₂ exhibit similarities and overlapping vibrational features, the PO₂ spectrum can be uniquely identified by an asymmetric stretching vibration at 1253 cm⁻¹. The POH spectrum is distinguished by a peak at 2301 cm⁻¹, arising from the interaction of phosphorus with a silanol hydrogen. The HPO spectrum features a characteristic peak at 2075 cm⁻¹, corresponding to the H–PO stretching vibration. Finally, PH₃ exhibits peaks at 2313 cm⁻¹, assigned to the PH stretching vibration.

5种含磷分子（PO、PO2、POH、HPO和PH3）在非晶二氧化硅上的吸附行为，不仅是星际硅酸盐尘埃颗粒的代表模型，也是在益生元和地球化学过程中起作用的陆地硅酸盐表面的代表模型，研究了它们的吸附和光谱特征。采用VASP框架内的色散校正密度泛函理论（DFT-D3）。计算出的吸附能均为负，表明吸附过程是放热和热力学有利的。分子间距离和贝德电荷证实了化学吸附是主要的相互作用模式，这与观察到的能量学一致。红外光谱进一步证明了吸附物质与二氧化硅表面之间形成了化学键。虽然PO和PO₂的光谱具有相似性和重叠的振动特征，但PO₂光谱可以通过1253 cm−1的不对称拉伸振动来唯一识别。POH光谱在2301 cm−1处有一个峰，是由磷与硅醇氢相互作用产生的。HPO光谱在2075 cm−1处有一个特征峰，对应于H-PO的拉伸振动。PH3在2313 cm−1处出现峰值，属于PH拉伸振动。

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引用次数: 0

First-principles investigation of phosphorus-rich Zintl phases X₄P₆ (X = K, Rb, Cs) for efficient visible-light-driven photocatalytic energy conversion 富磷Zintl相X₄P₆（X = K, Rb, Cs）高效可见光催化能量转换的第一性原理研究

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry

Pub Date : 2025-12-29 DOI: 10.1016/j.comptc.2025.115653

S. Bendouda, M. Batouche, M.E.A. El Goutni, T. Seddik, Baltach Hadj

This comprehensive study employs density functional theory (DFT) calculations within the WIEN2k framework to systematically explore the structural, electronic, optical, and photocatalytic properties of phosphorus-rich Zintl-phase compounds X₄P₆, where X represents the alkali metals K, Rb, or Cs. Electronic structure calculations using the HSE hybrid functional reveal indirect bandgaps ranging from 1.23 eV (K₄P₆) to 1.40 eV (Cs₄P₆), optimally positioned for visible-light absorption, with enhanced charge-carrier dynamics driven by orbital hybridization. Optical characterizations demonstrate strong absorption coefficients exceeding 20 × 10⁴ cm⁻¹ across the visible spectrum, with K₄P₆ exhibiting superior light-harvesting efficiency. Band-edge alignment calculations confirm thermodynamic suitability for spontaneous water splitting, with conduction-band minima at −0.11 to −0.20 eV and valence-band maxima at +1.12 to +1.20 eV versus the normal hydrogen electrode (NHE), with Cs₄P₆ offering optimal overpotentials. This extended analysis, enriched with in-depth physical insights into lattice dynamics, charge transport, and optical interactions, establishes X₄P₆ compounds as highly promising candidates for sustainable solar-to‑hydrogen energy conversion, with potential for further optimization through compositional engineering.

这项综合研究采用WIEN2k框架内的密度泛函理论（DFT）计算，系统地探索了富磷锌相化合物X₄P₆的结构、电子、光学和光催化性能，其中X代表碱金属K、Rb或Cs。利用HSE杂化泛函进行的电子结构计算显示，间接带隙范围从1.23 eV （K₄P₆）到1.40 eV （Cs₄P₆），最适合可见光吸收，轨道杂化驱动的电荷载流子动力学增强。光学表征表明，在可见光谱上，K₄P₆的吸收系数超过20 × 104 cm−1，具有优异的光捕获效率。带边校准计算证实了自发水分解的热力学适用性，与普通氢电极（NHE）相比，导带最小值为- 0.11至- 0.20 eV，价带最大值为+1.12至+1.20 eV， Cs₄P₆提供最佳过电位。这一扩展分析，丰富了对晶格动力学、电荷输运和光相互作用的深入物理见解，确立了X₄P₆化合物作为可持续太阳能到氢能源转换的极有前途的候选者，并有可能通过成分工程进一步优化。

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引用次数: 0