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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
Chemical Physics Letters Pub Date : 2026-04-01 Epub Date: 2026-02-04 DOI: 10.1016/j.cplett.2026.142682
Cesar A. de Mello
{"title":"Spectral origins of frontier-orbital inversions in atoms and molecules","authors":"Cesar A. de Mello","doi":"10.1016/j.cplett.2026.142682","DOIUrl":"10.1016/j.cplett.2026.142682","url":null,"abstract":"<div><div>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, <span><math><mrow><mrow><mo>(</mo><mi>n</mi><mspace></mspace><mo>−</mo><mspace></mspace><mn>1</mn><mo>)</mo></mrow><mi>d</mi></mrow></math></span>, <span><math><mrow><mn>4</mn><mi>f</mi></mrow></math></span>, <span><math><mrow><mn>5</mn><mi>f</mi></mrow></math></span>, <span><math><mi>σ</mi></math></span> and <span><math><mi>π</mi></math></span> 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, <span><math><msup><mrow><mi>NO</mi></mrow><mrow><mo>+</mo></mrow></msup></math></span> and <span><math><msub><mrow><mi>O</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span>, providing a unified, physically interpretable origin for inorganic irregularities without invoking empirical rules or system-specific assumptions.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"888 ","pages":"Article 142682"},"PeriodicalIF":3.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116462","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
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
Chemical Physics Letters Pub Date : 2026-04-01 Epub Date: 2026-02-03 DOI: 10.1016/j.cplett.2026.142689
Chong Li
{"title":"Impacts of intramolecular dynamic disorder on photoexcitation in a single non-fullerene acceptor molecule","authors":"Chong Li","doi":"10.1016/j.cplett.2026.142689","DOIUrl":"10.1016/j.cplett.2026.142689","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"888 ","pages":"Article 142689"},"PeriodicalIF":3.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116463","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
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
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
{"title":"Luminescence-based ratiometric oxygen sensing utilizing natural wood and Gd(III) complex with significantly enhanced sensitivity and interference resistance","authors":"Yujie Niu,&nbsp;Zhongxing Zhang,&nbsp;Ting Liu","doi":"10.1016/j.cplett.2026.142693","DOIUrl":"10.1016/j.cplett.2026.142693","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"888 ","pages":"Article 142693"},"PeriodicalIF":3.1,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116464","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 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
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
{"title":"First-principles insights into the structure and interaction mechanisms of hydrated Mg2+ clusters","authors":"Jiale Kong ,&nbsp;Mengxu Li ,&nbsp;Lingwen Meng ,&nbsp;Ruili Shi ,&nbsp;Yan Su","doi":"10.1016/j.cplett.2026.142657","DOIUrl":"10.1016/j.cplett.2026.142657","url":null,"abstract":"<div><div>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 Mg<sup>2+</sup>, we investigated Mg<sup>2+</sup>(H<sub>2</sub>O)<sub><em>n</em></sub> (<em>n</em> = 1–10) clusters using a comprehensive genetic algorithm and density functional theory. The results show that the Mg<sup>2+</sup>–water distance increases with <em>n</em>, 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 Mg<sup>2+</sup>.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"887 ","pages":"Article 142657"},"PeriodicalIF":3.1,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146025317","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
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
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
{"title":"Gaussian boson sampling of ozone: Vibronic structure of the Wulf band and intersystem crossing rate","authors":"K. Khoroshkin ,&nbsp;R. Valiyev ,&nbsp;L.I. Valiulina ,&nbsp;V.N. Cherepanov ,&nbsp;E.O. Filippova ,&nbsp;B.S. Merzlikin","doi":"10.1016/j.cplett.2026.142658","DOIUrl":"10.1016/j.cplett.2026.142658","url":null,"abstract":"<div><div>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 <span><math><mrow><msub><mi>k</mi><mi>ISC</mi></msub></mrow></math></span> ranges from 10<sup>9</sup> to 10<sup>10</sup> s<sup>−1</sup> 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.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"887 ","pages":"Article 142658"},"PeriodicalIF":3.1,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146025327","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
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
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
{"title":"Revisiting aromaticity of five-membered rings: a dissected ring current analysis","authors":"Rodrigo Báez-Grez ,&nbsp;Ricardo Pino-Rios","doi":"10.1016/j.cplett.2026.142680","DOIUrl":"10.1016/j.cplett.2026.142680","url":null,"abstract":"<div><div>The aromaticity of five-membered heteroaromatic rings (C₄H₄X, X = CH<sup>−</sup>, 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<sub>π</sub>) establish the order: CH<sup>−</sup> &gt; NH &gt; S &gt; Se &gt; O &gt; Te. This trend is explained as heteroatom's ability to donate its lone-pair, electronegativity, and conjugation efficiency. Comparison with NICS(1)<sub>zz,π</sub> aligns with RCS<sub>π</sub>, whereas total NICS is distorted by the other contributions, highlighting RCS<sub>π</sub> as a more reliable aromaticity descriptor, particularly for heterocycles containing heavier elements.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"887 ","pages":"Article 142680"},"PeriodicalIF":3.1,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074914","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
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
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)
{"title":"Perfect spin-filtering effect and multifunctional spin logic gates in planar four-coordinate Fe complexes-based molecular device","authors":"Mei Wang (王梅) ,&nbsp;Xingwen Zheng (郑兴稳) ,&nbsp;Bin Cui (崔彬) ,&nbsp;Juan Pei (裴娟) ,&nbsp;Haitong Wang (王海烔) ,&nbsp;Xi Zuo (左希) ,&nbsp;Desheng Liu (刘德胜)","doi":"10.1016/j.cplett.2026.142677","DOIUrl":"10.1016/j.cplett.2026.142677","url":null,"abstract":"<div><div>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 (FeN<sub>4</sub>) 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.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"887 ","pages":"Article 142677"},"PeriodicalIF":3.1,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074889","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
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
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
{"title":"Nonphotochemical shockwave-induced nucleation and time-resolved anisotropic crystal growth in KNO₃ solutions","authors":"Watheq Al-Basheer ,&nbsp;Musab Hashim ,&nbsp;Ahmed M. El-Zohry ,&nbsp;Abdulaziz Aljalal ,&nbsp;Said M. Al Azar ,&nbsp;Khaled Gasmi","doi":"10.1016/j.cplett.2026.142683","DOIUrl":"10.1016/j.cplett.2026.142683","url":null,"abstract":"<div><div>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/cm<sup>2</sup>), 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.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"887 ","pages":"Article 142683"},"PeriodicalIF":3.1,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146170696","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
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
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
{"title":"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]","authors":"Rachid Hsissou ,&nbsp;Fouad Benhiba ,&nbsp;Meriam El Aboubi ,&nbsp;Said Abbout ,&nbsp;Zakaria Benzekri ,&nbsp;Zaki Safi ,&nbsp;Mourad Rafik ,&nbsp;Hanane Bahaj ,&nbsp;Meriyam Kaba ,&nbsp;Mouhsine Galai ,&nbsp;Nuha Wazzan ,&nbsp;Samir Briche ,&nbsp;Said Boukhris ,&nbsp;Abdelkader Zarrouk ,&nbsp;Mohamed EbnTouhami ,&nbsp;Mohamed Rafik","doi":"10.1016/j.cplett.2026.142638","DOIUrl":"10.1016/j.cplett.2026.142638","url":null,"abstract":"","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"887 ","pages":"Article 142638"},"PeriodicalIF":3.1,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146025325","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
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
Chemical Physics Letters Pub Date : 2026-03-16 Epub Date: 2026-01-07 DOI: 10.1016/j.cplett.2026.142647
Zahra Jamshidi
{"title":"Addressing modeling challenges for metal clusters: Determining spin-multiplicity and accelerating self-consistent field convergence","authors":"Zahra Jamshidi","doi":"10.1016/j.cplett.2026.142647","DOIUrl":"10.1016/j.cplett.2026.142647","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"887 ","pages":"Article 142647"},"PeriodicalIF":3.1,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074890","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
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