Physical Chemistry Chemical Physics最新文献_第9页

A Quantitatively Constrained Framework for Defect Identification in Oxides: Application to Cr3+ Centers in PbTiO3 氧化物缺陷识别的定量约束框架：在PbTiO3中Cr3+中心的应用

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2026-03-17 DOI: 10.1039/d6cp00148c

Yavuz Berk Dinler, Muhammed Acikgoz

Identifying paramagnetic defect centers in ferroelectric oxides is challenging due to the large configurational space of dopants and the strong sensitivity of spectroscopic signatures to local structure. In this work, we present a unified framework for assigning Cr 3+ defect centers in PbTiO 3 by combining machine-learning-based structural optimization with quantitatively constrained zero-field splitting (ZFS) analysis. A comprehensive set of substitutional and charge-compensated Cr defect models was constructed and relaxed using the CHGNet interatomic potential. Local Cr-O coordination geometries were then extracted and used as input for superposition-model calculations of ZFS parameters, which were systematically fitted to experimental EPR data under strict bounds on both intrinsic and structural variations. By jointly evaluating ZFS mismatches, parameter stability, and independent structural quality metrics, we establish objective criteria to discriminate physically plausible defect configurations from unphysical ones. This analysis enables consistent assignment of the experimentally observed EPR centers C1-C4 to a limited subset of defect models, while excluding the majority of bulk-like configurations. In particular, the dominant bulk center C1 is reproduced by low-distortion Ti-site substitution models involving long-range defect interactions. Although certain bulk-based configurations provide partial agreement for the nanopowder-specific center C4, the absence of a fully consistent bulk solution indicates a size-dependent origin associated with more complex local environment, such as surface-related coordination effects. The methodology introduced here is general and transferable, providing a robust route for defect identification in functional oxides that integrates machine-learning structural fidelity with physically constrained spectroscopic modeling.

由于掺杂物的大结构空间和光谱特征对局部结构的高灵敏度，确定铁电氧化物中的顺磁缺陷中心具有挑战性。在这项工作中，我们将基于机器学习的结构优化与定量约束零场分裂（ZFS）分析相结合，提出了一个统一的pbtio3中Cr 3+缺陷中心分配框架。建立了一套完整的取代和电荷补偿Cr缺陷模型，并利用CHGNet原子间电位进行了松弛。然后提取局部Cr-O配位几何，并将其作为ZFS参数叠加模型计算的输入，在严格的内禀和结构变化边界下，系统地拟合到实验EPR数据中。通过联合评估ZFS不匹配、参数稳定性和独立的结构质量度量，我们建立了客观的标准来区分物理上合理的缺陷配置和非物理的缺陷配置。这种分析能够将实验观察到的EPR中心C1-C4一致地分配到缺陷模型的有限子集，同时排除了大多数的体状配置。特别是，主要的体中心C1是通过低畸变的钛位取代模型再现的，该模型涉及远程缺陷相互作用。尽管某些基于体积的配置为纳米粉末特异性中心C4提供了部分一致性，但缺乏完全一致的体积溶液表明，与更复杂的局部环境（如表面相关的配位效应）相关的尺寸依赖性来源。这里介绍的方法是通用的和可转移的，为功能性氧化物的缺陷识别提供了一个强大的途径，将机器学习结构保真度与物理约束的光谱建模相结合。

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引用次数: 0

Determining Molecular Structures of Cytochrome P450 and Its Complex Associated with Model Cell Membranes 细胞色素P450及其与模型细胞膜相关复合物的分子结构测定

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2026-03-17 DOI: 10.1039/d6cp00572a

Guangyao Wu, Wen Guo, Pei Yang, Rui Huang, Ayyalusamy Ramamoorthy, Zhan Chen

The lipid membrane assisted interaction between cytochrome P450 (CYP450) and its reductase (CPR) plays a significant role in many biochemical reactions and drug metabolism.Previous solution and solid-state studies have shown the importance of lipid bilayer on the structural folding of CYP450 and the electrostatic interactions between the soluble domains and the hydrophobic interactions between the transmembrane helical domains of CYP450 and CPR using bicelles and nanodiscs. In this study we report an effective way to determine both the conformation and orientation of the truncated microsomal CYP450 2B4 associated with lipid membranes, and its orientation transition when binding to a truncated flavin mononucleotide binding domain of CPR. The developed methodology combines measurements using sum frequency generation vibrational spectroscopy and attenuated total reflectance -Fourier transform infrared spectroscopy, and computational data interpretation, which is powerful and generally applicable to reveal the interfacial structures of protein complexes in physiologically relevant environments.

脂膜辅助细胞色素P450 （CYP450）与其还原酶（CPR）的相互作用在许多生化反应和药物代谢中起着重要作用。先前的溶液和固态研究表明，脂质双分子层对CYP450结构折叠的重要性，以及CYP450和CPR的可溶结构域之间的静电相互作用和跨膜螺旋结构域之间的疏水相互作用。在这项研究中，我们报道了一种有效的方法来确定与脂膜相关的截短微粒体CYP450 2B4的构象和取向，以及它与截断的CPR黄素单核苷酸结合域结合时的取向转变。所开发的方法结合了和频产生振动光谱和衰减全反射-傅里叶变换红外光谱的测量，以及计算数据解释，该方法强大且普遍适用于揭示生理相关环境中蛋白质复合物的界面结构。

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引用次数: 0

Cu-doped P₃S-I monolayer: selective and robust toxic gas detection in ambient environments. cu掺杂P3S-I单层：环境中选择性和鲁棒性有毒气体检测。

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2026-03-17 DOI: 10.1039/d5cp04684j

Xuan Li, Li Shao, Yuantao He, Yan Li, Jiehu Cui

The effects of Cu doping and the adsorption of six small molecules (NO, NO₂, NH₃, CO, SO₂, and H₂S) on the geometric structure and electronic properties of a two-dimensional P₃S-I monolayer were investigated by density functional theory (DFT). The results reveal that, compared to the intrinsic P₃S-I material with a bandgap of 1.665 eV, the bandgaps of both the doped and small molecule adsorption systems decrease. Among them, the change of bandgaps of NO, NO₂, and SO₂ adsorption systems is more significant. Furthermore, calculations of adsorption energy, Bader charge, differential charge density, density of states, and crystal orbital Hamilton population (COHP) validate that these three gas molecules have a pronounced influence on the electronic properties of P₃S-I, making them effective for detection.

利用密度泛函理论（DFT）研究了Cu掺杂和6种小分子（NO、NO2、NH3、CO、SO2和H2S）的吸附对二维P3S-I单层膜几何结构和电子性能的影响。结果表明，与带隙为1.665 eV的本征P3S-I材料相比，掺杂和小分子吸附体系的带隙都减小了。其中，NO、NO2和SO2吸附体系的带隙变化更为显著。此外，吸附能、Bader电荷、差分电荷密度、态密度和晶体轨道Hamilton居群（COHP）的计算验证了这三种气体分子对P3S-I的电子性质有显著影响，使它们能够有效地用于检测。

引用次数: 0

Thermodynamics and electronic structure evolution from single-H2 adsorption to stepwise hydrogen loading of Fe metalloporphyrin. 铁金属卟啉从单h2吸附到分步载氢的热力学和电子结构演变。

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2026-03-17 DOI: 10.1039/d6cp00311g

Mustafa Kurban,İskender Muz

Designing molecular motifs that can bind hydrogen strongly enough for uptake yet weakly enough for deliverable release remains a central challenge for adsorptive storage. Here, we use dispersion-corrected density functional theory to map the complete hydrogen-loading pathway of an iron porphyrin (Fe-MP, Fe metalloporphyrin) scaffold from n = 1 to 20 H2, connecting optimized configurations to adsorption energetics, thermodynamics and electronic-structure fingerprints. A clear hierarchy of adsorption environments emerges: the first H2 binds at the Fe center with a short Fe⋯H2 contact and an elongated H-H bond (1.65 Å and 0.80 Å, respectively), while subsequent H2 molecules populate progressively weaker sites surrounding the macrocycle. This transition is reflected in thermodynamics, with the mean adsorption energy collapsing from -0.47 eV per H2 at n = 1 to -0.03 eV per H2 at n = 20, accompanied by a marked reduction in desorption temperature from 599 K to 42 K. Despite the increase in gravimetric capacity to an upper bound of 9.97 wt% at full loading, the high-coverage reservoir is therefore intrinsically weakly bound and most relevant under pressure-assisted and/or cryogenic conditions. Charge analysis and projected density of states reveal progressive polarization without disruptive changes to the host electronic backbone, with an essentially invariant frontier gap (5.88-5.93 eV) across loading. Real-space interaction fingerprints from RDG-sign(λ2)ρ maps confirm a shift from localized attractive contributions at low coverage to dispersive confinement and steric crowding at high coverage. Together, these results separate capacity from usability in a chemically transparent adsorbent and provide a transferable design rule for computational materials discovery: high uptake must be accompanied by the multiplication of intermediate-strength binding motifs to move the storage manifold beyond a purely dispersion-dominated outer shell.

设计能够结合氢的分子基元，使其足够强以供吸收，但又足够弱以供释放，这仍然是吸附储存的核心挑战。本研究利用色散校正的密度泛函理论绘制了铁卟啉（Fe- mp, Fe metalloporphyrin）支架从n = 1到20 H2的完整载氢路径，并将优化构型与吸附热力学、热力学和电子结构指纹图谱联系起来。一个清晰的吸附环境层次结构出现了：第一个H2结合在Fe中心，具有短的Fe， H2接触和拉长的H-H键（分别为1.65 Å和0.80 Å），而随后的H2分子填充在大环周围逐渐变弱的位置。这种转变反映在热力学中，平均吸附能从n = 1时的-0.47 eV / H2下降到n = 20时的-0.03 eV / H2，同时解吸温度从599 K显著降低到42 K。尽管在满负荷状态下，重测能力的上限为9.97 wt%，但高覆盖层的储层本质上是弱约束的，在压力辅助和/或低温条件下最相关。电荷分析和态的投影密度显示，在没有破坏主电子骨干的情况下，材料呈渐进式极化，在加载过程中边界隙（5.88-5.93 eV）基本不变。来自RDG-sign(λ2)ρ图的真实空间相互作用指纹证实了从低覆盖下的局部吸引力贡献到高覆盖下的色散限制和空间拥挤的转变。总之，这些结果将化学透明吸附剂的容量与可用性分开，并为计算材料的发现提供了可转移的设计规则：高吸收率必须伴随着中等强度结合基序的乘法，以使存储歧管超越纯粹的分散主导的外壳。

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引用次数: 0

Organophosphate Ethyl Paraoxon on Ag and Au Surfaces: A Density Functional Theory Perspective 银和金表面上的有机磷酸酯乙基对氧磷：密度泛函理论的视角

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2026-03-17 DOI: 10.1039/d5cp03632a

Hang Hu, Jiří Hostaš, Mohammad Sajjad Ghaemi, Junan Lin, Shiliang Wang, Anguang Hu, Hsu Kiang Ooi

Organophosphates, a class of organic compounds containing phosphorus, have garnered considerable attention due to their widespread applications in agriculture. Understanding their optical properties is crucial for food safety, toxicity analysis, and early detection. In this work, the optical properties of an organophosphate containing paraoxon moiety and its interactions with gold and silver surfaces are investigated using density functional theory. The differences between physisorption and chemisorption of ethyl paraoxon, a commonly used model organophosphate compound, on metal surfaces explain discrepancies observed in the reported experimental Raman spectra.

有机磷酸盐是一类含磷的有机化合物，由于其在农业中的广泛应用而引起了人们的广泛关注。了解它们的光学性质对食品安全、毒性分析和早期检测至关重要。本文利用密度泛函理论研究了含对氧离子的有机磷酸盐的光学性质及其与金、银表面的相互作用。乙酯对氧磷（一种常用的模型有机磷化合物）在金属表面的物理吸附和化学吸附的差异解释了实验拉曼光谱中观察到的差异。

引用次数: 0

High-Efficiency Solar Water Splitting and Tunable Excitons in the 2D RhTeCl Monolayer 二维RhTeCl单层中高效太阳能水分解和可调激子

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2026-03-17 DOI: 10.1039/d6cp00374e

Xian-huan Wu, Xiaofei Sheng, Cenglin Yao, Wenyu Fang, Xiao-Xiao Rao, Jiafu Wang

Photocatalytic water splitting is a pivotal pathway for sustainable hydrogen production, where 2D materials are highly promising due to their exceptional properties. Here we systematically investigate the potential of monolayer RhTeCl for photocatalytic water splitting through first-principles calculations. Our results reveal that the monolayer exhibits remarkable stability, with a high predicted thermodynamic stability up to 1000 K. It possesses a direct bandgap of 2.26 eV, whose band edges align ideally with the redox potentials for water splitting. Notably, the monolayer demonstrates carrier mobilities ranging from 101.12 to 774.61 cm2/V s, and a superior predicted solar-to-hydrogen conversion efficiency of up to 12%, surpassing the current experimental records. Furthermore, we uncover intriguing tunable excitonic properties in this monolayer. Both external strain and electric fields can effectively modulate the exciton binding energy, with the electric field exerting a more pronounced influence. Importantly, under these external perturbations, the exciton binding energy (Eb) and the direct quasiparticle bandgap (Eg) are found to approximately adhere to the empirical relationship Eb≈0.25Eg. These findings position 2D RhTeCl as a compelling and multifunctional platform for high-efficiency solar-driven water splitting and optoelectronic applications.

光催化水分解是可持续制氢的关键途径，其中二维材料由于其特殊的性能而非常有前途。在这里，我们通过第一性原理计算系统地研究了单层RhTeCl光催化水分解的潜力。我们的研究结果表明，单分子膜表现出显著的稳定性，在1000 K时具有很高的预测热力学稳定性。它具有2.26 eV的直接带隙，其带边缘与水分解的氧化还原电位理想地对齐。值得注意的是，该单层材料的载流子迁移率在101.12至774.61 cm2/V s之间，预计太阳能到氢的转换效率高达12%，超过了目前的实验记录。此外，我们发现在这种单层中有趣的可调谐激子特性。外加应变和电场都能有效地调节激子结合能，其中电场的影响更为明显。重要的是，在这些外部扰动下，发现激子结合能（Eb）和直接准粒子带隙（Eg）近似遵循经验关系Eb≈0.25Eg。这些发现将2D RhTeCl定位为高效太阳能驱动的水分解和光电子应用的引人注目的多功能平台。

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引用次数: 0

The study of hydrogen adsorption-induced topological surface state in-out hop in MgB2 nodal-line semimetals via physics-informed Bayesian optimization. 基于物理贝叶斯优化的氢吸附诱导MgB2节点线半金属拓扑表面态进出跳的研究。

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2026-03-16 DOI: 10.1039/d5cp03713a

Qinchi Yue,Kun Bu,Ruzhi Wang,Changhao Wang

Hydrogen adsorption critically modulates topological surface states (TSSs) in the nodal-line semimetal MgB2. We identify a threshold adsorption distance of 2.212 Å between H and surface B atoms, triggering an abrupt relocation of TSSs from inside to outside nodal-lines, referred to as "in-out hop." Beyond this distance, H weakly hybridizes with TSSs; subcritical adsorption induces the mutation of TSSs via covalent interactions. To resolve this phenomenon with quantum accuracy and data efficiency, we develop physics-informed Bayesian optimization (PIBO). PIBO unifies Dirac-derived constraints (TSSs' non-negativity and energy monotonicity) with sparse ab initio data, training a distance-dependent two-body model. With only 43 training points, PIBO achieves meV-level TSS reconstruction and establishes E1+θ as an effective energy descriptor for coupled bands. This framework bypasses many-body intractability by embedding physical boundaries into ML workflows, enabling predictive engineering of adsorption-tuned topological devices. The PIBO methodology bridges ab initio precision and computational efficiency for accelerated quantum materials design.

氢吸附临界调节节点线半金属MgB2的拓扑表面态（tss）。我们确定H和表面B原子之间的阈值吸附距离为2.212 Å，触发tss从内部到外部节点线的突然迁移，称为“输入-输出跳”。在此距离之外，H与TSSs弱杂化；亚临界吸附通过共价相互作用诱导tss突变。为了以量子精度和数据效率解决这一现象，我们开发了物理通知贝叶斯优化（PIBO）。PIBO将dirac导出约束（tss的非负性和能量单调性）与稀疏从头算数据统一起来，训练距离相关的两体模型。PIBO仅用43个训练点就实现了mev级的TSS重构，并建立了E1+θ作为耦合波段的有效能量描述子。该框架通过将物理边界嵌入ML工作流程来绕过多体难解性，从而实现吸附调谐拓扑设备的预测工程。PIBO方法桥梁从头算精度和计算效率的加速量子材料设计。

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引用次数: 0

Radiative cooling of isolated Al$_5^-$ cluster ions observed on ultralong timescales as a test case for the validity of the harmonic cascade model 在超长时间尺度上观察到孤立Al$_5^-$簇离子的辐射冷却，作为谐波级联模型有效性的检验案例

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2026-03-16 DOI: 10.1039/d6cp00329j

Yehuda Ben Shabo, Damian Muell, Viviane Charlotte Schmidt, Klaus Blaum, Paul Fischer, Sebastian George, Manfred Grieser, Florian Grussie, Oded Heber, Mark Alan Iron, Oldrich Novotny, Lutz Schweikhard, Andreas Wolf, Daniel Zajfman, Aigars Znotins, Holger Kreckel, Yoni Toker

While discussing the vibrational radiative cooling of isolated cluster molecules, it is common to apply statistical models based on the density of vibrational states and calculated transition strengths. In the current work, we put this assumption to the test by studying the cooling rates of isolated AlFiveM ions across very long timescales ranging up to $2,000$~s. To this end, we stored AlFiveM ions in the Cryogenic Storage Ring (CSR) and monitored their internal excitation by laser-induced delayed electron emission. We find that once the internal energy drops below the first electronically excited state, the cooling rates scale linearly with energy. Our results are consistent with the calculated vibrational relaxation rates through the emission of infrared photons, based on the harmonic cascade model, thus validating quantitatively the assumption of a statistical cooling process for the relaxation of small cluster molecules with infrared-active vibrational modes.

在讨论孤立团簇分子的振动辐射冷却时，通常采用基于振动态密度和计算跃迁强度的统计模型。在目前的工作中，我们通过研究孤立的 al55m离子在非常长的时间尺度上的冷却速率（高达$ 2,000 $~s）来验证这一假设。为此，我们将AlFiveM离子储存在低温储存环（CSR）中，并通过激光诱导的延迟电子发射监测其内部激发。我们发现，一旦内能低于第一电子激发态，冷却速率与能量成线性关系。我们的结果与基于谐波级联模型计算的红外光子发射的振动弛豫率一致，从而定量地验证了具有红外主动振动模式的小簇分子弛豫的统计冷却过程的假设。

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引用次数: 0

Insights into the molecular association of aqueous deep eutectic solvents using cell permeability. 利用细胞渗透性洞察水相深共晶溶剂的分子关联。

IF 3.3 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2026-03-16 DOI: 10.1039/d5cp03195h

Saffron J Bryant,Miyah N Awad,Amanda N Abraham,Izabela Miłogrodzka,Tamar L Greaves,Gary Bryant

Deep eutectic solvents are increasingly of interest across a range of fields, from energy storage, to cryopreservation, to chemical extraction. However, many fundamental characteristics are still unknown, or worse, assumed, leaving many questions unanswered and unasked. One of these is whether or not the components of deep eutectic solvents associate with each other when in dilute solutions. In this paper shrink-swell experiments are used to examine the permeability of a deep eutectic solvent composed of proline and ethylene glycol, using two mammalian cell types. Using the deep eutectic composition, as well as other ratios of the components, it was found that proline did not permeate while ethylene glycol does permeate. This demonstrates that at least for this deep eutectic solvent, the components act independently when in dilute solution. This has implications for the fundamental understanding of solvent behaviour as well as specific applications such as cryopreservation which rely on cell permeation of active agents.

深共晶溶剂在能源储存、低温保存、化学萃取等领域受到越来越多的关注。然而，许多基本特征仍然是未知的，或者更糟的是，假设，留下了许多未解决和未提出的问题。其中之一是在稀溶液中，深共晶溶剂的组分是否相互结合。本文采用收缩膨胀实验来研究由脯氨酸和乙二醇组成的深共晶溶剂的渗透性，实验采用两种哺乳动物细胞类型。利用深共晶组成，以及组分的其他比例，发现脯氨酸不渗透，而乙二醇渗透。这表明，至少对于这种深共晶溶剂，各组分在稀溶液中独立作用。这对溶剂行为的基本理解以及依赖于活性物质细胞渗透的低温保存等特定应用具有重要意义。

引用次数: 0

Thermoelectric properties of lead halide Janus layers - a theoretical investigation. 卤化铅Janus层热电特性的理论研究。

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics

Pub Date : 2026-03-16 DOI: 10.1039/d5cp04987c

A E Sudheer, M Vallinayagam, G Tejaswini, A Kumar, M Posselt, C Kamal, M Zschornak, D Murali

Thermoelectric materials offer a promising route for efficient heat-to-power conversion. In search of materials functional at high and low operating temperatures, we investigate the thermoelectric properties of two-dimensional lead halide Janus layers (JLs) using density functional theory. The electronegativity difference between halides in JLs significantly modulates the electronic structure, particularly the strong Pb-F bonding in PbIF JLs leads to pronounced band curvature and a unique direct bandgap. Estimated through three-phonon interactions, the lattice thermal conductivity is intrinsically low, primarily due to acoustic phonon contributions and suppressed optical phonon transport. The thermoelectric coefficients are enhanced with carrier doping, resulting in figures of merit as high as 1.48 at room temperature and up to 4.93 at elevated temperatures. Up to 30% of heat-energy conversion efficiency is acheived at 1000 K in PbIBr JL. These findings establish two-dimensional lead halide Janus layers, particularly the PbIBr layer, as optimal candidates for thermoelectric conversion, and the insights into their elemental and electronic characteristics offer a valuable basis for the future design of high-performance lead-based thermoelectric materials.

热电材料为有效的热-电转换提供了一条有前途的途径。为了寻找在高温和低温下功能的材料，我们利用密度泛函理论研究了二维卤化铅Janus层（JLs）的热电特性。JLs中卤化物的电负性差异显著地调节了电子结构，特别是PbIF JLs中强的Pb-F键导致了明显的带曲率和独特的直接带隙。通过三声子相互作用估计，晶格热导率本质上是低的，主要是由于声子贡献和抑制光学声子输运。热电系数随着载流子的掺杂而增强，在室温下达到1.48，在高温下达到4.93。在PbIBr JL中，在1000 K下可实现高达30%的热能转换效率。这些发现确定了二维卤化铅Janus层，特别是PbIBr层，是热电转换的最佳候选者，并且对其元素和电子特性的见解为未来设计高性能铅基热电材料提供了有价值的基础。

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引用次数: 0