Chemical Physics Letters最新文献

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Spectral origins of frontier-orbital inversions in atoms and molecules 原子和分子中前沿轨道反转的光谱起源

IF 3.1 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters

Pub Date : 2026-04-01 Epub Date: 2026-02-04 DOI: 10.1016/j.cplett.2026.142682

Cesar A. de Mello

Frontier-orbital inversions in atoms and molecules are usually treated as isolated anomalies, yet they follow a single underlying mechanism. This work shows that ns,

(n - 1) d

4 f

5 f

σ

and

π

orbitals form smooth spectral branches whose curvature, penetration, shielding and relativistic response determine their ordering. When two branches with contrasting radial character become nearly degenerate, the reduced gap collapses and the HOMO/LUMO identity flips. This branch-competition framework reproduces classic anomalies in Pd, Pt/Au, Eu/Yb, U/Pu, CO,

{NO}^{+}

and

O_{2}

, providing a unified, physically interpretable origin for inorganic irregularities without invoking empirical rules or system-specific assumptions.

原子和分子的前沿轨道反转通常被视为孤立的异常现象，但它们遵循单一的潜在机制。这项工作表明，ns, (n−1)d, 4f, 5f， σ和π轨道形成光滑的光谱分支，其曲率，穿透，屏蔽和相对论响应决定了它们的顺序。当两个具有不同径向特征的分支接近简并时，约简间隙坍塌，HOMO/LUMO同一性翻转。该分支竞争框架再现了Pd、Pt/Au、Eu/Yb、U/Pu、CO、NO+和O2中的经典异常，为无机不规则性提供了统一的、物理上可解释的起源，而无需调用经验规则或系统特定假设。

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引用次数: 0

Impacts of intramolecular dynamic disorder on photoexcitation in a single non-fullerene acceptor molecule 分子内动力学紊乱对单个非富勒烯受体分子光激发的影响

IF 3.1 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters

Pub Date : 2026-04-01 Epub Date: 2026-02-03 DOI: 10.1016/j.cplett.2026.142689

Chong Li

Intrinsic dynamic disorders can detrimentally affect performance of the organic solar cells (OSCs). However, low-energy nature and ultrafast time scale of dynamic disorders make them difficult to be traced experimentally. In this study, by applying the photoexcitation dynamics with the onsite energetic dynamic disorder (OEDD) and transfer integral dynamic disorder (TIDD) included, impacts of intramolecular dynamic disorders on photoexcitation properties of the NFA molecule are theoretically studied. The TIDD is found to play a more significant influence on the absorption spectrum through modulation of the energy gap. Furthermore, the non-uniform dynamic disorder effects in a NFA molecule are further discussed.

内在动力学紊乱会严重影响有机太阳能电池的性能。然而，由于其低能量和超快时间尺度的特性，使其难以在实验上进行追踪。本研究采用包含现场能量动力学紊乱（OEDD）和传递积分动力学紊乱（TIDD）的光激发动力学，从理论上研究了分子内动力学紊乱对NFA分子光激发特性的影响。发现TIDD通过调制能隙对吸收光谱有更显著的影响。进一步讨论了NFA分子中的非均匀动态无序效应。

引用次数: 0

Luminescence-based ratiometric oxygen sensing utilizing natural wood and Gd(III) complex with significantly enhanced sensitivity and interference resistance 利用天然木材和Gd（III）配合物的基于发光的比例氧传感，具有显著增强的灵敏度和抗干扰性

IF 3.1 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters

Pub Date : 2026-04-01 Epub Date: 2026-02-03 DOI: 10.1016/j.cplett.2026.142693

Yujie Niu, Zhongxing Zhang, Ting Liu

For the first time, a self-referenced ratiometric oxygen sensor (OS-HBC) using eco-friendly balsa wood via a simple fabrication process was successfully developed. Through optimization of the preparation, the sensitivity of the sensor was improved by 51-fold, and the underlying mechanism for this enhancement has been revealed. The sensor exhibits excellent photostability under fluctuating light sources, varying humidity levels, and during continuous operation. With a rapid response time of 3.7 s and stable performance maintained over a 10-day period, OS-HBC exhibits significant potential for real-time oxygen sensing across the entire oxygen concentration range in complex and dynamically changing environments.

通过简单的制造工艺，首次成功开发了一种使用环保轻木的自参考比例氧传感器（OS-HBC）。通过优化制备，传感器的灵敏度提高了51倍，并揭示了这种增强的潜在机制。该传感器在波动光源、不同湿度水平和连续工作期间表现出优异的光稳定性。OS-HBC具有3.7 s的快速响应时间和超过10天的稳定性能，在复杂和动态变化的环境中显示出在整个氧气浓度范围内实时氧气传感的巨大潜力。

引用次数: 0

First-principles insights into the structure and interaction mechanisms of hydrated Mg2+ clusters 水合Mg2+团簇结构和相互作用机制的第一性原理研究

IF 3.1 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters

Pub Date : 2026-03-16 Epub Date: 2026-01-16 DOI: 10.1016/j.cplett.2026.142657

Jiale Kong , Mengxu Li , Lingwen Meng , Ruili Shi , Yan Su

Aqueous batteries attract attention due to their cost-effectiveness, high safety, and environmental friendliness. In aqueous systems, multivalent cations show higher capacity and energy density than monovalent ones. To gain insight into the initial hydration of Mg²⁺, we investigated Mg²⁺(H₂O)_n (n = 1–10) clusters using a comprehensive genetic algorithm and density functional theory. The results show that the Mg²⁺–water distance increases with n, the coordination number stabilizes at six, and additional water molecules have minimal impact. Binding-energy and charge analyses reveal a transition from strong ion–water interactions to hydrogen-bond stabilization. This work clarifies the atomic-scale hydration mechanism of Mg²⁺.

水电池因其性价比高、安全性高、环境友好等特点而备受关注。在水体系中，多价阳离子比一价阳离子表现出更高的容量和能量密度。为了深入了解Mg2+的初始水化作用，我们使用综合遗传算法和密度泛函理论研究了Mg2+(H2O)n （n = 1-10）簇。结果表明：Mg2+ -水的距离随着n的增加而增加，配位数稳定在6，而额外的水分子对Mg2+ -水的影响最小。结合能和电荷分析揭示了从强离子-水相互作用到氢键稳定的转变。本文阐明了Mg2+的原子水化机理。

引用次数: 0

Gaussian boson sampling of ozone: Vibronic structure of the Wulf band and intersystem crossing rate 臭氧的高斯玻色子采样：伍尔夫带的振动结构和系统间交叉率

IF 3.1 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters

Pub Date : 2026-03-16 Epub Date: 2026-01-17 DOI: 10.1016/j.cplett.2026.142658

K. Khoroshkin , R. Valiyev , L.I. Valiulina , V.N. Cherepanov , E.O. Filippova , B.S. Merzlikin

Gaussian Boson Sampling (GBS) was applied to describe photophysics of ozone. One million Franck–Condon configurations were generated to model the Wulf-band vibronic progression and to compute the intersystem crossing rate constant. The calculated value of

k_{ISC}

ranges from 10⁹ to 10¹⁰ s⁻¹ depending on the approach used. Although ozone has an unusually large vibrational frequency ratio between the initial and final electronic states and non-negligible Duschinsky rotation, neglecting both effects in the linear-coupled approximation yields nearly identical results. The study demonstrates that GBS can yield accurate vibronic spectra and ISC rate constants at a computational cost inaccessible to classical summations.

采用高斯玻色子采样（GBS）描述臭氧的光物理现象。生成了一百万个frank - condon构型来模拟武尔夫带的振动过程并计算系统间的穿越速率常数。根据不同的计算方法，kISC的取值范围为109 ~ 1010s−1。虽然臭氧在初始和最终电子态之间具有异常大的振动频率比和不可忽略的Duschinsky旋转，但在线性耦合近似中忽略这两种效应会产生几乎相同的结果。研究表明，GBS可以得到精确的振动谱和ISC速率常数，而计算成本是经典求和无法达到的。

引用次数: 0

Revisiting aromaticity of five-membered rings: a dissected ring current analysis 重新审视五元环的芳香性：解剖环电流分析

IF 3.1 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters

Pub Date : 2026-03-16 Epub Date: 2026-01-24 DOI: 10.1016/j.cplett.2026.142680

Rodrigo Báez-Grez , Ricardo Pino-Rios

The aromaticity of five-membered heteroaromatic rings (C₄H₄X, X = CH⁻, NH, O, S, Se, Te) was evaluated using dissected ring current strength (RCS) calculations via the GIAO-CD method. Although total RCS values suggest thiophene is more aromatic than pyrrole, π-electron contributions (RCS_π) establish the order: CH⁻ > NH > S > Se > O > Te. This trend is explained as heteroatom's ability to donate its lone-pair, electronegativity, and conjugation efficiency. Comparison with NICS(1)_zz,π aligns with RCS_π, whereas total NICS is distorted by the other contributions, highlighting RCS_π as a more reliable aromaticity descriptor, particularly for heterocycles containing heavier elements.

采用GIAO-CD法计算解剖环电流强度（RCS），评价了五元杂芳环（C₄H₄X, X = CH−,nh0， S, Se, Te）的芳构性。虽然总RCS值表明噻吩比吡咯更芳香，但π电子贡献值（RCSπ）确定的顺序为：CH−>； NH > S > Se > O > Te。这一趋势被解释为杂原子提供其孤对、电负性和共轭效率的能力。与NICS(1)zz相比，π与RCSπ一致，而总NICS被其他贡献扭曲，突出RCSπ是更可靠的芳性描述符，特别是对于含有重元素的杂环。

引用次数: 0

Perfect spin-filtering effect and multifunctional spin logic gates in planar four-coordinate Fe complexes-based molecular device 平面四坐标铁配合物分子器件中完美的自旋滤波效应和多功能自旋逻辑门

IF 3.1 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters

Pub Date : 2026-03-16 Epub Date: 2026-01-24 DOI: 10.1016/j.cplett.2026.142677

Mei Wang (王梅) , Xingwen Zheng (郑兴稳) , Bin Cui (崔彬) , Juan Pei (裴娟) , Haitong Wang (王海烔) , Xi Zuo (左希) , Desheng Liu (刘德胜)

In the field of future information technology, high-performance spin devices are crucial. We model spin-dependent electron transport in molecular junctions with a planar four-coordinate Fe complex (FeN₄) sandwiched between two armchair carbon nanotube (CNT) electrodes in series or parallel configurations. Using density functional theory and non-equilibrium Green's function formalisms, simulations reveal perfect spin-filtering effects. Moreover, magnetic coupling between two Fe atoms induces distinct spin-polarized current-voltage characteristics in series and parallel devices. Based on these findings, we design multifunctional AND, NOT, and OR spin logic gates, offering an attractive, novel approach for high-performance molecular spin devices.

在未来的信息技术领域，高性能的自旋器件是至关重要的。我们用平面四坐标铁配合物（FeN4）以串联或并联的方式夹在两个扶手椅碳纳米管（CNT）电极之间，模拟分子结中自旋相关的电子传递。利用密度泛函理论和非平衡格林函数形式，模拟显示了完美的自旋过滤效果。此外，两个铁原子之间的磁耦合在串联和并联器件中产生了不同的自旋极化电流-电压特性。基于这些发现，我们设计了多功能的AND， NOT和OR自旋逻辑门，为高性能分子自旋器件提供了一种有吸引力的新方法。

引用次数: 0

Nonphotochemical shockwave-induced nucleation and time-resolved anisotropic crystal growth in KNO₃ solutions KNO₃溶液中非光化学冲击波诱导成核和时间分辨各向异性晶体生长

IF 3.1 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters

Pub Date : 2026-03-16 Epub Date: 2026-01-28 DOI: 10.1016/j.cplett.2026.142683

Watheq Al-Basheer , Musab Hashim , Ahmed M. El-Zohry , Abdulaziz Aljalal , Said M. Al Azar , Khaled Gasmi

We demonstrate shockwave-induced nucleation and crystallization in supersaturated aqueous KNO₃ using a single 7 ns, 532 nm laser pulse on a metallic substrate. The pulse launches shockwaves at low peak power densities (2.18–2.73 GW/cm²), triggering rapid synchronized nucleation. Crystal morphology and changes in length and width were monitored as a function of time. Crystal dimensions increased linearly with time, with enhanced longitudinal growth yielding anisotropic, needle-like morphologies. At fixed power density, longitudinal growth scaled linearly with concentration, whereas lateral growth was suppressed near the spontaneous-crystallization threshold. Nearly constant growth rates indicate interface-limited kinetics and yield narrow, Gaussian-like size distributions.

我们在金属衬底上使用单个7 ns， 532 nm的激光脉冲证明了在过饱和水态KNO₃中冲击波诱导的成核和结晶。脉冲以低峰值功率密度（2.18-2.73 GW/cm2）发射冲击波，触发快速同步成核。晶体形态和长度和宽度的变化被监测为时间的函数。晶体尺寸随时间线性增加，纵向生长增强，产生各向异性，针状形态。在固定功率密度下，纵向生长随浓度呈线性增长，而横向生长在自发结晶阈值附近受到抑制。几乎恒定的生长速率表明界面动力学受限，产率窄，类似高斯的尺寸分布。

引用次数: 0

Retraction notice to “Synthesis and performance of two ecofriendly epoxy resins as a highly efficient corrosion inhibition for carbon steel in 1 M HCl solution: DFT, RDF, FFV and MD approaches” [Chem. Phys. Lett. 806 (2022) 139995] “两种环保环氧树脂在1 M盐酸溶液中作为碳钢的高效缓蚀剂的合成和性能：DFT， RDF， FFV和MD方法”的撤回通知[化学]。理论物理。Lett. 806 (2022) 139995]

IF 3.1 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters

Pub Date : 2026-03-16 Epub Date: 2026-01-23 DOI: 10.1016/j.cplett.2026.142638

Rachid Hsissou , Fouad Benhiba , Meriam El Aboubi , Said Abbout , Zakaria Benzekri , Zaki Safi , Mourad Rafik , Hanane Bahaj , Meriyam Kaba , Mouhsine Galai , Nuha Wazzan , Samir Briche , Said Boukhris , Abdelkader Zarrouk , Mohamed EbnTouhami , Mohamed Rafik

引用次数: 0

Addressing modeling challenges for metal clusters: Determining spin-multiplicity and accelerating self-consistent field convergence 解决金属簇的建模挑战：确定自旋多重性和加速自洽场收敛

IF 3.1 3区化学 Q3 CHEMISTRY, PHYSICAL

Chemical Physics Letters

Pub Date : 2026-03-16 Epub Date: 2026-01-07 DOI: 10.1016/j.cplett.2026.142647

Zahra Jamshidi

Modeling small metal clusters with density functional theory (DFT) presents challenges in identifying the lowest-energy spin state and achieving robust SCF convergence. A method is introduced to determine the spin polarization that minimizes the difference between the chemical potentials of two Fermi levels, allowing direct identification of the lowest-energy spin state. This approach is applied to iron and cobalt clusters with intermediate spin states, and reproducing stable spin polarization consistent with separate single-point calculations. In addition, SCF convergence accelerators, including Pulay’s DIIS variants, linear-expansion shooting techniques (LISTs), and their combinations (MESA), are systematically evaluated for their efficiency in improving convergence.

用密度泛函理论（DFT）建模小金属团簇，在确定最低能量自旋态和实现鲁棒自旋场收敛方面面临挑战。介绍了一种确定自旋极化的方法，该方法使两个费米能级的化学势差最小，从而可以直接识别最低能量的自旋态。该方法应用于具有中间自旋态的铁和钴簇，并再现了与单独的单点计算一致的稳定自旋极化。此外，SCF收敛加速器，包括Pulay的DIIS变体，线性扩展射击技术（LISTs）及其组合（MESA），系统地评估了它们在提高收敛性方面的效率。

引用次数: 0

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