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High-resolution spectroscopy of [H,C,N]+: I. Rotationally resolved vibrational bands of HCN+ and HNC. [H,C,N]+的高分辨率光谱:1 . HCN+和HNC的旋转分辨振动带。
IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2026-01-28 DOI: 10.1039/d5cp04201a
Philipp C Schmid, Samuel J P Marlton, Weslley G D P Silva, Thomas Salomon, János Sarka, Sven Thorwirth, Oskar Asvany, Stephan Schlemmer

Rovibrational spectra of the open-shell linear cations HCN+ (X̃2Π) and HNC+ (X̃2Σ+) are measured with leak-out spectroscopy in cryogenic 22-pole ion traps. The fundamental ν1 C-H stretching vibration of HCN+ is found at 3056.3412(1) cm-1 and the lower energy Renner-Teller (RT) component (Σ) of the ν1 + ν2 combination band is found at 3340.8480(2) cm-1. The resulting effective RT vibrational frequency of ≈300 cm-1 inferred from the comparison of these two bands indicates a large Renner-Teller splitting for HCN+. For HNC+, the ν1 N-H stretching vibration is found at 3407.9136(4) cm-1, much higher than expected from previous matrix work. Thanks to the rotational resolution of these infrared measurements, spectroscopic constants for the electronic fine-structure, molecular rotation, centrifugal distortion, Λ-doubling and spin-rotation interaction have been determined for the vibrational ground and excited states with high confidence. The infrared spectrum of HCN+ is rather rich and contains more bands including, e.g., the electronic à ← X̃ transition. The analysis of this band and the pure rotational spectrum of HCN+ will be the subject of further publications.

用泄漏光谱法在低温22极离子阱中测量了开壳线性阳离子HCN+ (X′2Π)和HNC+ (X′2Σ+)的振动光谱。HCN+的基本ν1 C-H伸缩振动位于3056.3412(1)cm-1, ν1 + ν2组合带的较低能量Renner-Teller (RT)分量(Σ)位于3340.8480(2)cm-1。从这两个波段的比较推断得到的有效RT振动频率约为300 cm-1,表明HCN+存在较大的Renner-Teller分裂。对于HNC+, ν1 N-H拉伸振动在3407.9136(4)cm-1处,远高于先前矩阵工作的预期。由于这些红外测量的旋转分辨率,电子精细结构、分子旋转、离心畸变、Λ-doubling和自旋-旋转相互作用的光谱常数已经以高置信度确定了振动基态和激发态。HCN+的红外光谱相当丰富,包含更多的波段,例如电子Ã←X→跃迁。对这一波段和HCN+的纯旋转光谱的分析将是进一步发表的主题。
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引用次数: 0
An Efficient Route to Glyceraldehyde (HOCH2CH(OH)CHO) — The Simplest Aldose — via Reactions of Carbon-Centered Radicals in Deep Space 深空碳中心自由基反应制备最简单醛糖——甘油醛(HOCH2CH(OH)CHO)的有效途径
IF 3.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2026-01-28 DOI: 10.1039/d5cp04397b
Joshua H. Marks, Jia Wang, Ryan C. Fortenberry, Ralf I. Kaiser
The simplest sugar — glyceraldehyde (HOCH2CH(OH)CHO) — represents a central molecule in the biochemistry of all lifeforms (glycolysis/gluconeogenesis). Linking photosynthesis and carbon fixation to sugar metabolism is fundamental to the liberation of energy from sugars and is the point at which glycolysis becomes exothermic — the pay-off phase. By exploiting isomer-selective photoionization reflectron time-of-flight mass spectrometry, glyceraldehyde and its energetic enol isomer 1,2,3-propenetriol (HOCH2C(OH)CHOH) are identified in situ during space-simulation experiments as reaction products of radicals formed in ethylene glycol (HOCH2CH2OH) and carbon monoxide (CO) interstellar model ices exposed to proxies for galactic cosmic rays. Isotopic substitution demonstrates the mechanism of sugar formation from molecules abundant in the interstellar medium. The stability of the carbon-centered radical intermediates formyl (HĊO) and 1,2-dihydroxyethyl (HOCH2ĊHOH) imply that reactions of carbon monoxide and methanol derivatives like ethylene glycol represent a facile, highly active mechanism of sugar production within ice coated interstellar grains in deep space.
最简单的糖-甘油醛(HOCH2CH(OH)CHO) -代表了所有生命形式(糖酵解/糖异生)的生物化学中心分子。将光合作用和碳固定与糖代谢联系起来,是从糖中释放能量的基础,也是糖酵解变成放热的点——回报阶段。利用异构体选择性光电离反射飞行时间质谱法,在空间模拟实验中原位鉴定了甘油醛及其高能烯醇异构体1,2,3-丙烯三醇(HOCH2C(OH)CHOH)是暴露于银河系宇宙射线代用物的乙二醇(HOCH2CH2OH)和一氧化碳(CO)星际模型冰中形成自由基的反应产物。同位素取代证明了星际介质中丰富的分子形成糖的机制。碳中心自由基中间体甲酰基(HĊO)和1,2-二羟乙基(HOCH2ĊHOH)的稳定性表明,一氧化碳和甲醇衍生物(如乙二醇)的反应代表了深空冰封星际颗粒中一个简单、高活性的制糖机制。
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引用次数: 0
Uncertainty-Aware Machine Learning-Based Prediction of Plasma Parameters in a Microwave Atmospheric Pressure Plasma Jet 基于不确定性感知机器学习的微波大气压等离子体射流等离子体参数预测
IF 3.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2026-01-28 DOI: 10.1039/d5cp04364f
Suryasunil Rath, Priyabrata Das, Pulak M Pandey, Satyananda Kar
Microwave atmospheric pressure plasma jets (MW-APPJs) exhibit significant potential for diverse applications, i.e., hydrogen production, CO2 dissociation, water treatment, material processing and waste treatment due to their stable operation at atmospheric pressure and generation of highly tunable reactive species. For effective utilization of MW-APPJs, a detailed understanding of the operational conditions that influence plasma parameters is essential. The present work proposes an uncertainty-aware, multi-output, interpretable supervised machine learning (ML) framework to predict eight plasma parameters, viz electron excitation temperature (Texc), electron number density (ne), four reactive species (OH, N2, Hα and O), gas temperature (Tg), and plume length. A dataset comprising 441 experimental runs was generated by varying input powers (700-1000 W), sliding short positions (0.95-1.05 λg/2) and argon flow rate (5-15 lpm). Six regression models namely k-nearest neighbours (KNN), extra trees (ET), random forest (RF), artificial neural networks (ANN), gradient boosting (GB), and extreme gradient boosting (XGB) were optimized using Bayesian hyperparameter tuning and evaluated using both accuracy and reliability metrics. While XGB achieved competitive pointwise accuracy, the optimized GB model emerged as the most balanced performer when predictive accuracy, calibration behaviour, and uncertainty reliability were jointly considered. On a held-out test set, the GB model achieved mean absolute percentage errors below 3% and R² values exceeding 0.97 across all plasma parameters. Bootstrap-based uncertainty quantification demonstrated near-nominal 90% prediction interval coverage with comparatively narrow uncertainty bounds, and calibration analysis confirmed statistically consistent uncertainty estimates. Experimental validation using 30 independent plasma operating conditions, separated into interpolated and extrapolated regimes, further confirmed robust generalization, with increased epistemic uncertainty appropriately accompanying extrapolative predictions. SHapley Additive exPlanations (SHAP) based interpretability analysis identified microwave power as the dominant controlling feature for most plasma parameters, while gas flow rate governed the intensity of OH emission. Overall, this uncertainty-aware ML framework provides a reliable foundation for data-driven plasma diagnostics and future optimization of MW-APPJ-based processes.
微波常压等离子体射流(MW-APPJs)由于其在常压下稳定运行和产生高度可调的反应物质,在制氢、CO2解离、水处理、材料加工和废物处理等领域具有巨大的应用潜力。为了有效利用MW-APPJs,详细了解影响等离子体参数的操作条件至关重要。目前的工作提出了一个不确定性感知,多输出,可解释的监督机器学习(ML)框架来预测八个等离子体参数,即电子激发温度(Texc),电子数密度(ne),四种反应物质(OH, N2, Hα和O),气体温度(Tg)和羽流长度。在不同的输入功率(700-1000 W)、滑动空位(0.95-1.05 λg/2)和氩气流量(5-15 lpm)下,生成了包含441个实验运行的数据集。使用贝叶斯超参数调优对k近邻(KNN)、额外树(ET)、随机森林(RF)、人工神经网络(ANN)、梯度增强(GB)和极端梯度增强(XGB) 6个回归模型进行了优化,并使用准确性和可靠性指标进行了评估。虽然XGB实现了具有竞争力的逐点精度,但当综合考虑预测精度、校准行为和不确定性可靠性时,优化后的GB模型表现出最平衡的性能。在固定测试集上,GB模型在所有等离子体参数上的平均绝对百分比误差低于3%,R²值超过0.97。基于bootstrap的不确定性量化显示出接近名义90%的预测区间覆盖率,不确定性界限相对较窄,校准分析证实了统计上一致的不确定性估计。实验验证使用30个独立的等离子体操作条件,分为内插和外推制度,进一步证实了稳健的泛化,增加了认知的不确定性,适当地伴随外推预测。基于SHapley加性解释(SHAP)的可解释性分析发现,微波功率是大多数等离子体参数的主要控制特征,而气体流速决定OH发射强度。总的来说,这种不确定性感知ML框架为数据驱动的等离子体诊断和基于mw - appj的流程的未来优化提供了可靠的基础。
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引用次数: 0
Experimentally confirmed ferroelectricity in organic compounds identified by database mining 实验证实了通过数据库挖掘识别的有机化合物中的铁电性
IF 3.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2026-01-27 DOI: 10.1039/d5cp03009a
Maximilian Litterst, Manjunath Balagopalan, Ramon Jannasch, Elin D Sødahl, Seyedmojtaba Seyedraoufi, Carl H. Gorbitz, Kristian Berland, Ola Nilsen, Martijn Kemerink
Compared to inorganic ferroelectrics, the breadth of polarization switching mechanisms in organic ferroelectrics is very broad and far from fully characterized or understood. Here, we experimentally investigate the absence or presence of ferroelectric properties in a selection of organic materials that have been identified by a data mining approach using heuristic measures to identify stretchability, aiming to assess the practical potential of this approach. From a set of 66 candidate materials, 4 were selected for detailed analysis. These were investigated structurally using powder X-ray diffraction and electrically, using capacitance-voltage spectroscopy and polarization hysteresis measurements. Despite large differences in stability and background conductivity, all compounds exhibited ferroelectric behavior at room temperature, with relatively large polarization values. Specifically, the ferroelectric properties of one material show a strong dependency on the ambient humidity, whereas another showed a strong coupling between background conductivity and ferroelectric switching. These effects are not yet fully understood and lie beyond the scope of this study. Of the remaining two compounds, one was found to be unstable at room temperature whereas the other displayed multiple polymorphs, complicating reproducibility and limiting their practical potential. Overall, these results confirm the relevance of the data mining prediction scheme and suggest that a significant fraction of the identified but so far untested materials may also be ferroelectric.
与无机铁电体相比,有机铁电体的极化开关机制的广度是非常广泛的,远未完全表征或理解。在这里,我们通过实验研究了通过数据挖掘方法确定的有机材料中铁电性质的缺失或存在,这些材料使用启发式方法来确定拉伸性,旨在评估该方法的实际潜力。从66份候选材料中,选取4份进行详细分析。利用粉末x射线衍射和电、电容电压光谱和极化迟滞测量对它们进行了结构研究。尽管稳定性和背景电导率有很大差异,但所有化合物在室温下都表现出铁电行为,具有相对较大的极化值。具体来说,一种材料的铁电特性表现出对环境湿度的强烈依赖,而另一种材料则表现出背景电导率和铁电开关之间的强烈耦合。这些影响尚未被完全理解,也超出了本研究的范围。在剩下的两种化合物中,一种在室温下是不稳定的,而另一种则表现出多重多态性,这使得可重复性变得复杂,限制了它们的实际应用潜力。总的来说,这些结果证实了数据挖掘预测方案的相关性,并表明已确定但迄今尚未测试的材料中有很大一部分也可能是铁电的。
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引用次数: 0
Electronic and magnetic properties modulated by nonvolatile switching in the multiferroic Cr2Cl3S3/Ga2O3 van der Waals heterostructure. 多铁Cr2Cl3S3/Ga2O3范德华异质结构中非易失性开关调制的电子和磁性能
IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2026-01-27 DOI: 10.1039/d5cp03967c
Jing-Jing He, Jun-Yi Gu, Qin-Yue Cao, Ling-Xiao Liu, Min Hua, Jia-Ren Yuan, Yan-Dong Guo, Xiao-Hong Yan

Two-dimensional multiferroic materials, which exhibit both ferroelectricity and ferromagnetism, have drawn significant interest due to their capability to control electronic and magnetic properties via polarization switching. In this work, we designed a multiferroic van der Waals heterostructure (vdWH) made of 2D ferromagnetic Cr2Cl3S3 and ferroelectric Ga2O3, and examined its structural, electronic, and magnetic properties through first-principles calculations. The results demonstrate that by manipulating the polarization state of Ga2O3, the Cr2Cl3S3(Cl)/Ga2O3 vdWH can reversibly switch between semiconductor and half-metal, whereas the Cr2Cl3S3(S)/Ga2O3 vdWH can transition reversibly between semiconductor and metal. These reversible transitions are attributed to the shift in band alignment induced by interlayer charge transfer. Notably, as the spintronic properties of the Cr2Cl3S3(S)/Ga2O3 vdWH change, its easy magnetization axis also switches from in-plane to out-of-plane. The switchable electrical control of heterostructures by ferroelectric Ga2O3 is nonvolatile. These findings are important for understanding ferroelectric control of spintronics and electromagnetic coupling and provide a potential route for developing multiferroic memory devices.

二维多铁性材料具有铁电性和铁磁性,由于其通过极化开关控制电子和磁性的能力而引起了人们的极大兴趣。在这项工作中,我们设计了由二维铁磁Cr2Cl3S3和铁电Ga2O3组成的多铁范德华异质结构(vdWH),并通过第一性原理计算考察了其结构、电子和磁性能。结果表明,通过控制Ga2O3的极化状态,Cr2Cl3S3(Cl)/Ga2O3 vdWH可以在半导体和半金属之间可逆转换,而Cr2Cl3S3(S)/Ga2O3 vdWH可以在半导体和半金属之间可逆转换。这些可逆转变是由于层间电荷转移引起的带对准偏移。值得注意的是,随着Cr2Cl3S3(S)/Ga2O3 vdWH自旋电子性质的变化,其易磁化轴也从平面内切换到平面外。铁电Ga2O3对异质结构的可切换电气控制是非挥发性的。这些发现对于理解自旋电子学和电磁耦合的铁电控制具有重要意义,并为开发多铁存储器件提供了一条潜在的途径。
{"title":"Electronic and magnetic properties modulated by nonvolatile switching in the multiferroic Cr<sub>2</sub>Cl<sub>3</sub>S<sub>3</sub>/Ga<sub>2</sub>O<sub>3</sub> van der Waals heterostructure.","authors":"Jing-Jing He, Jun-Yi Gu, Qin-Yue Cao, Ling-Xiao Liu, Min Hua, Jia-Ren Yuan, Yan-Dong Guo, Xiao-Hong Yan","doi":"10.1039/d5cp03967c","DOIUrl":"https://doi.org/10.1039/d5cp03967c","url":null,"abstract":"<p><p>Two-dimensional multiferroic materials, which exhibit both ferroelectricity and ferromagnetism, have drawn significant interest due to their capability to control electronic and magnetic properties <i>via</i> polarization switching. In this work, we designed a multiferroic van der Waals heterostructure (vdWH) made of 2D ferromagnetic Cr<sub>2</sub>Cl<sub>3</sub>S<sub>3</sub> and ferroelectric Ga<sub>2</sub>O<sub>3</sub>, and examined its structural, electronic, and magnetic properties through first-principles calculations. The results demonstrate that by manipulating the polarization state of Ga<sub>2</sub>O<sub>3</sub>, the Cr<sub>2</sub>Cl<sub>3</sub>S<sub>3</sub>(Cl)/Ga<sub>2</sub>O<sub>3</sub> vdWH can reversibly switch between semiconductor and half-metal, whereas the Cr<sub>2</sub>Cl<sub>3</sub>S<sub>3</sub>(S)/Ga<sub>2</sub>O<sub>3</sub> vdWH can transition reversibly between semiconductor and metal. These reversible transitions are attributed to the shift in band alignment induced by interlayer charge transfer. Notably, as the spintronic properties of the Cr<sub>2</sub>Cl<sub>3</sub>S<sub>3</sub>(S)/Ga<sub>2</sub>O<sub>3</sub> vdWH change, its easy magnetization axis also switches from in-plane to out-of-plane. The switchable electrical control of heterostructures by ferroelectric Ga<sub>2</sub>O<sub>3</sub> is nonvolatile. These findings are important for understanding ferroelectric control of spintronics and electromagnetic coupling and provide a potential route for developing multiferroic memory devices.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146049639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Eu³⁺-induced passivation and charge-transport modulation in Cs₂FeCl₅·H₂O single crystals and evaporated thin films for photodetectors Eu³⁺在Cs₂FeCl₅·H₂O单晶和蒸发薄膜中诱导钝化和电荷输运调制,用于光电探测器
IF 3.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2026-01-27 DOI: 10.1039/d5cp04307g
Chen Wang, Yu Li, Jiayi Ren, Huimeng Shen, Qi Sun, Hui Yan, Xinpei Li, Huawei Zhou, Xianxi Zhang, Federico Rosei, Jun Zhang
In recent years, metal halide compounds have been widely studied as a class of semiconductor materials with superior optoelectronic characteristics. In particular, rare metal doping has been observed to affect the properties of metal halide compounds, yet the mechanisms are not understood. In this study, we incorporated Eu³⁺ into the Cs₂FeCl₅·H₂O crystal system, aiming to thoroughly investigate its comprehensive effects on the material's structural, optical, and electrical properties, and ultimate performance as a photodetector. The results indicate that both the Cs₂FeCl₅·H₂O and Eu doping Cs₂FeCl₅·H₂O single crystals belong to the orthorhombic crystal system with the space group Cmcm (No.63). The Eu3+ ion is successfully incorporated into the host lattice, which result in the lattice expansion phenomenon observed in X-ray Diffraction (XRD), bandgap widening, increasing the resistance and emission intensity of the samples in photoluminescence. This positive outcome is attributed to the effective passivation realized by Eu3+ incorporation. The dark current density of the photodetector devices based on the Eu3+- doping decreased significantly from the undoped value of 18.3 ± 3.0 to 2.1 ± 1.2 μA/cm². Smaller dark current and high bulk resistance can effectively prevent semiconductor devices from breakdown, making them applicable in the field of high-power semiconductors. This work offers insight for the future design and development of metal halide photoelectronic materials with low noise and high response speed.
近年来,金属卤化物化合物作为一类具有优异光电特性的半导体材料受到了广泛的研究。特别是,稀有金属掺杂对金属卤化物的性质有影响,但其作用机制尚不清楚。在这项研究中,我们将Eu³⁺结合到Cs₂FeCl₅·H₂O晶体体系中,旨在深入研究其对材料结构、光学和电学性能的综合影响,以及作为光电探测器的最终性能。结果表明,Cs₂FeCl₅·H₂O和Eu掺杂Cs₂FeCl₅·H₂O单晶都属于具有空间群Cmcm (No.63)的正交晶系。Eu3+离子成功地加入到主体晶格中,导致x射线衍射(XRD)中观察到的晶格膨胀现象,带隙变宽,提高了样品的光致发光电阻和发射强度。这一积极结果归因于Eu3+掺入实现的有效钝化。Eu3+-掺杂的光电探测器器件的暗电流密度从未掺杂的18.3±3.0 μA/cm²显著降低到2.1±1.2 μA/cm²。较小的暗电流和较高的体电阻能有效防止半导体器件击穿,适用于大功率半导体领域。本研究为未来设计和开发低噪声、高响应速度的金属卤化物光电子材料提供了参考。
{"title":"Eu³⁺-induced passivation and charge-transport modulation in Cs₂FeCl₅·H₂O single crystals and evaporated thin films for photodetectors","authors":"Chen Wang, Yu Li, Jiayi Ren, Huimeng Shen, Qi Sun, Hui Yan, Xinpei Li, Huawei Zhou, Xianxi Zhang, Federico Rosei, Jun Zhang","doi":"10.1039/d5cp04307g","DOIUrl":"https://doi.org/10.1039/d5cp04307g","url":null,"abstract":"In recent years, metal halide compounds have been widely studied as a class of semiconductor materials with superior optoelectronic characteristics. In particular, rare metal doping has been observed to affect the properties of metal halide compounds, yet the mechanisms are not understood. In this study, we incorporated Eu³⁺ into the Cs₂FeCl₅·H₂O crystal system, aiming to thoroughly investigate its comprehensive effects on the material's structural, optical, and electrical properties, and ultimate performance as a photodetector. The results indicate that both the Cs₂FeCl₅·H₂O and Eu doping Cs₂FeCl₅·H₂O single crystals belong to the orthorhombic crystal system with the space group Cmcm (No.63). The Eu3+ ion is successfully incorporated into the host lattice, which result in the lattice expansion phenomenon observed in X-ray Diffraction (XRD), bandgap widening, increasing the resistance and emission intensity of the samples in photoluminescence. This positive outcome is attributed to the effective passivation realized by Eu3+ incorporation. The dark current density of the photodetector devices based on the Eu3+- doping decreased significantly from the undoped value of 18.3 ± 3.0 to 2.1 ± 1.2 μA/cm². Smaller dark current and high bulk resistance can effectively prevent semiconductor devices from breakdown, making them applicable in the field of high-power semiconductors. This work offers insight for the future design and development of metal halide photoelectronic materials with low noise and high response speed.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"33 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057022","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
First-principles investigation of the insulator-metal transition in layered NaNiO2: coupled electronic and lattice effects. 层状纳米二氧化硅中绝缘体-金属跃迁的第一性原理研究:耦合电子和晶格效应。
IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2026-01-27 DOI: 10.1039/d5cp03746h
Xiaohong Chu, Zhenyi Jiang, Ping Guo, Jiming Zheng, Xiaodong Zhang

NaNiO2 is a layered material composed of alternating NaO6 and NiO6 octahedra, which undergoes an insulator-metal transition (IMT) from a monoclinic insulating phase to a metallic phase at approximately 480 K. Although this phase transition has been experimentally observed, its microscopic mechanism remains unclear, particularly regarding the role of Jahn-Teller (JT) distortion and the nature of the structural dynamics during the transition. In this work, we carry out a comprehensive first-principles study to address these issues. Our results show that the IMT is primarily driven by the gradual disappearance of the JT distortion of Ni3+, which restores the eg orbital degeneracy and enables electronic delocalization. Furthermore, potential energy surface analysis and phonon spectrum calculations reveal that this process follows a displacive phase transition pathway, consistent with experimental observations. These findings provide, for the first time, a theoretical explanation of the microscopic mechanism underlying the IMT in NaNiO2, thereby clarifying its structural-electronic interplay and offering new insights into the phase transition behavior of transition-metal oxides for future material applications.

纳米二氧化钛是一种由NaO6和NiO6交替八面体组成的层状材料,在大约480 K的温度下,从单斜绝缘相到金属相发生绝缘体-金属相变(IMT)。虽然这种相变已经被实验观察到,但其微观机制尚不清楚,特别是关于Jahn-Teller (JT)畸变的作用和转变过程中结构动力学的性质。在这项工作中,我们开展了一个全面的第一性原理研究来解决这些问题。我们的研究结果表明,IMT主要是由Ni3+的JT畸变逐渐消失驱动的,它恢复了eg轨道简并并使电子离域成为可能。此外,势能表面分析和声子谱计算表明,这一过程遵循位移相变途径,与实验观察结果一致。这些发现首次从理论上解释了纳米二氧化钛中IMT的微观机制,从而阐明了其结构-电子相互作用,并为过渡金属氧化物的相变行为提供了新的见解,为未来的材料应用提供了新的见解。
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引用次数: 0
Yttrium-doped lithium and potassium clusters: magnetic superatoms and their interaction with hydrogen 掺钇锂和钾簇:磁性超原子及其与氢的相互作用
IF 3.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2026-01-27 DOI: 10.1039/d5cp04393j
Henry Nicole González-Ramírez, Zeferino Gómez-Sandoval, Gururaj Kudur Jayaprakash, Juan Pablo Mojica-Sánchez, Roberto Flores-Moreno, Kayim Pineda-Urbina
In this study, we explored the energetic, structural, and magnetic properties of yttrium-doped lithium and potassium clusters using density functional theory combined with Born–Oppenheimer molecular dynamics simulations. The analysis revealed magnetic superatoms such as K9Y2 (μ = 5μB) with a frontier configuration analogous to Fe+. Global reactivity descriptors, particularly the low hardness values (η), identified K12Y, K11Y2, and K13 as the most reactive potassium clusters, while the analogous Li12Y, Li11Y2, and Li13 were also selected for subsequent hydrogen interaction analyses. The most stable hydrogen–cluster structures extracted from Born–Oppenheimer molecular dynamics at 300 K were reoptimized including dispersion corrections to compute adsorption and Gibbs free energies. The resulting complexes were analyzed through QTAIM, ELF, and Laplacian electron density maps, complemented by CM5 charge analysis. These results reveal predominant molecular physisorption across the Y-doped systems, with localized polarized chemisorption only in Li12Y. Overall, yttrium doping enhances magnetic polarization, energetic stability, and structural resilience of alkali-metal clusters, which retain their superatomic character and near-icosahedral frameworks under hydrogen exposure.
在这项研究中,我们利用密度泛函理论结合Born-Oppenheimer分子动力学模拟,探索了钇掺杂锂和钾簇的能量、结构和磁性能。分析发现,K9Y2 (μ = 5μB)等磁性超原子具有类似Fe+的边界构型。整体反应性描述符,特别是低硬度值(η),确定K12Y, K11Y2和K13是最具反应性的钾簇,而类似的Li12Y, Li11Y2和Li13也被选择用于后续的氢相互作用分析。从Born-Oppenheimer分子动力学中提取的最稳定的氢簇结构在300 K下进行了重新优化,包括色散校正,以计算吸附和吉布斯自由能。通过QTAIM, ELF和Laplacian电子密度图对所得配合物进行了分析,并辅以CM5电荷分析。这些结果揭示了主要的分子物理吸附贯穿y掺杂体系,与局部极化化学吸收仅在Li12Y。总体而言,钇掺杂增强了碱金属团簇的磁极化、能量稳定性和结构弹性,在氢暴露下保持了其超原子特性和近二十面体框架。
{"title":"Yttrium-doped lithium and potassium clusters: magnetic superatoms and their interaction with hydrogen","authors":"Henry Nicole González-Ramírez, Zeferino Gómez-Sandoval, Gururaj Kudur Jayaprakash, Juan Pablo Mojica-Sánchez, Roberto Flores-Moreno, Kayim Pineda-Urbina","doi":"10.1039/d5cp04393j","DOIUrl":"https://doi.org/10.1039/d5cp04393j","url":null,"abstract":"In this study, we explored the energetic, structural, and magnetic properties of yttrium-doped lithium and potassium clusters using density functional theory combined with Born–Oppenheimer molecular dynamics simulations. The analysis revealed magnetic superatoms such as K<small><sub>9</sub></small>Y<small><sub>2</sub></small> (<em>μ</em> = 5<em>μ</em><small><sub>B</sub></small>) with a frontier configuration analogous to Fe<small><sup>+</sup></small>. Global reactivity descriptors, particularly the low hardness values (<em>η</em>), identified K<small><sub>12</sub></small>Y, K<small><sub>11</sub></small>Y<small><sub>2</sub></small>, and K<small><sub>13</sub></small> as the most reactive potassium clusters, while the analogous Li<small><sub>12</sub></small>Y, Li<small><sub>11</sub></small>Y<small><sub>2</sub></small>, and Li<small><sub>13</sub></small> were also selected for subsequent hydrogen interaction analyses. The most stable hydrogen–cluster structures extracted from Born–Oppenheimer molecular dynamics at 300 K were reoptimized including dispersion corrections to compute adsorption and Gibbs free energies. The resulting complexes were analyzed through QTAIM, ELF, and Laplacian electron density maps, complemented by CM5 charge analysis. These results reveal predominant molecular physisorption across the Y-doped systems, with localized polarized chemisorption only in Li<small><sub>12</sub></small>Y. Overall, yttrium doping enhances magnetic polarization, energetic stability, and structural resilience of alkali-metal clusters, which retain their superatomic character and near-icosahedral frameworks under hydrogen exposure.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"72 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A highly active Au/In2O3 catalyst for the reverse water gas shift reaction. 一种高活性Au/In2O3反水气转换反应催化剂。
IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2026-01-27 DOI: 10.1039/d5cp04442a
Yuxue Zhao, Linlin Wu, Liangkai Xu, Rui Zou, Chang-Jun Liu

Supported gold catalysts are fundamentally and practically important for hydrogenation reactions due to their unique electronic properties and catalytic activity. In this work, Au nanoparticles were successfully deposited onto an In2O3 support via a deposition-precipitation method to form a Au/In2O3 catalyst, which was subsequently evaluated for CO2 hydrogenation under atmospheric pressure. This catalyst exhibits outstanding low-temperature activity for the reverse water gas shift (RWGS) reaction, achieving a CO2 conversion of 21.3%, a CO selectivity of 100%, and a CO formation rate of 0.30 mmolCO gcat-1 min-1 at 350 °C. Characterization results reveal that Au nanoparticles are uniformly dispersed on the In2O3 surface, accompanied by charge transfer from Au to the In2O3 support. This strong electronic metal-support interaction (EMSI) results in the formation of positively charged Auδ+ species, which facilitates H2 dissociation. Meanwhile, the generation of surface oxygen vacancies on In2O3 is promoted, enhancing CO2 adsorption and activation. These synergistic effects between Au nanoparticles and In2O3 account for the superior RWGS activities of the Au/In2O3 catalyst.

负载型金催化剂由于其独特的电子性质和催化活性,在氢化反应中具有重要的基础和实践意义。在这项工作中,通过沉积-沉淀方法,将Au纳米颗粒成功沉积在In2O3载体上,形成Au/In2O3催化剂,随后在常压下评估其CO2加氢性能。该催化剂在反水气变换(RWGS)反应中表现出优异的低温活性,在350℃下,CO2转化率为21.3%,CO选择性为100%,CO生成速率为0.30 mmolCO gcat-1 min-1。表征结果表明,Au纳米颗粒均匀分布在In2O3表面,并伴有电荷从Au向In2O3载体的转移。这种强烈的电子金属-载体相互作用(EMSI)导致带正电的Auδ+物质的形成,从而促进H2的解离。同时,促进了In2O3表面氧空位的生成,增强了CO2的吸附和活化。Au纳米颗粒与In2O3之间的协同效应是Au/In2O3催化剂具有优异的RWGS活性的原因。
{"title":"A highly active Au/In<sub>2</sub>O<sub>3</sub> catalyst for the reverse water gas shift reaction.","authors":"Yuxue Zhao, Linlin Wu, Liangkai Xu, Rui Zou, Chang-Jun Liu","doi":"10.1039/d5cp04442a","DOIUrl":"https://doi.org/10.1039/d5cp04442a","url":null,"abstract":"<p><p>Supported gold catalysts are fundamentally and practically important for hydrogenation reactions due to their unique electronic properties and catalytic activity. In this work, Au nanoparticles were successfully deposited onto an In<sub>2</sub>O<sub>3</sub> support <i>via</i> a deposition-precipitation method to form a Au/In<sub>2</sub>O<sub>3</sub> catalyst, which was subsequently evaluated for CO<sub>2</sub> hydrogenation under atmospheric pressure. This catalyst exhibits outstanding low-temperature activity for the reverse water gas shift (RWGS) reaction, achieving a CO<sub>2</sub> conversion of 21.3%, a CO selectivity of 100%, and a CO formation rate of 0.30 mmol<sub>CO</sub> g<sub>cat</sub><sup>-1</sup> min<sup>-1</sup> at 350 °C. Characterization results reveal that Au nanoparticles are uniformly dispersed on the In<sub>2</sub>O<sub>3</sub> surface, accompanied by charge transfer from Au to the In<sub>2</sub>O<sub>3</sub> support. This strong electronic metal-support interaction (EMSI) results in the formation of positively charged Au<sup><i>δ</i>+</sup> species, which facilitates H<sub>2</sub> dissociation. Meanwhile, the generation of surface oxygen vacancies on In<sub>2</sub>O<sub>3</sub> is promoted, enhancing CO<sub>2</sub> adsorption and activation. These synergistic effects between Au nanoparticles and In<sub>2</sub>O<sub>3</sub> account for the superior RWGS activities of the Au/In<sub>2</sub>O<sub>3</sub> catalyst.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146049623","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Low-Cost Calculation and Analysis of 2D IR Spectra of Model Diiron Trinitrosyl Complexes in the NO Stretch Region with Vibrational Perturbation Theory 用振动摄动理论低成本计算和分析NO拉伸区三硝基二铁配合物的二维红外光谱
IF 3.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2026-01-27 DOI: 10.1039/d5cp03578c
Hayden A Moran, Abigail F. Moody, Mark A Boyer, Paul Garrett, Manuel Quiroz, Sarnali Sanfui, Marcetta Y. Darensbourg, Carlos Baiz, Daniel P. Tabor
Two-dimensional infrared spectroscopy offers unique capabilities for probing vibrational coupling in complex metal–ligand systems. In this paper, we combine two-dimensional infrared spectroscopy with vibrational perturbation theory to investigate vibrational coupling in a diiron trinitrosyl complex across three stable redox states. Although these systems are challenging for electronic structure methods, we demonstrate that key features of experimental 2D IR spectra can be accurately reproduced using reduced-dimensional anharmonic calculations with a small harmonic frequency scaling. Analysis reveals that N–O stretching modes maintain high locality across all redox states, with coupling patterns that directly reflect variations in Fe–N bond strength. Using curvilinear coordinate analysis, we demonstrate that these differences result from systematic changes in cubic anharmonic force constants rather than mode delocalization. Our results establish N–O stretches as sensitive probes of metal–ligand bonding strength, expanding the toolkit for studying biologically relevant nitrosyl complexes.
二维红外光谱为探测复杂金属配体系统中的振动耦合提供了独特的能力。本文将二维红外光谱与振动摄动理论相结合,研究了三硝基二铁配合物在三种稳定氧化还原态上的振动耦合。尽管这些系统对电子结构方法具有挑战性,但我们证明了实验二维红外光谱的关键特征可以使用具有小谐波频率缩放的降维非调和计算精确再现。分析表明,N-O拉伸模式在所有氧化还原态中都保持高局域性,其耦合模式直接反映了Fe-N键强度的变化。利用曲线坐标分析,我们证明了这些差异是由三次非调和力常数的系统变化而不是模态离域引起的。我们的研究结果建立了N-O拉伸作为金属配体结合强度的敏感探针,扩展了研究生物相关亚硝基复合物的工具包。
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Physical Chemistry Chemical Physics
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