Pub Date : 2026-02-04DOI: 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, , , , and 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, and , providing a unified, physically interpretable origin for inorganic irregularities without invoking empirical rules or system-specific assumptions.
{"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":"2026-02-04","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}
Pub Date : 2026-02-03DOI: 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.
{"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":"2026-02-03","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}
Pub Date : 2026-02-03DOI: 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.
{"title":"Luminescence-based ratiometric oxygen sensing utilizing natural wood and Gd(III) complex with significantly enhanced sensitivity and interference resistance","authors":"Yujie Niu, Zhongxing Zhang, 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":"2026-02-03","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}
Pub Date : 2026-01-27DOI: 10.1016/j.cplett.2026.142681
Haoran Ma , Yongchun Li , Nan Yang , Siyi Wang , Xiatiguli Kahaer , Mei Xiang , Bumaliya Abulimiti , Xiaoning Wang
2,6-Dihydroxybenzaldehyde (2,6-DHBA), featuring ortho phenolic hydroxyl groups, exhibits notable antioxidant properties. However, the influence of substituents and solvent polarity on its ESIPT behavior and radical scavenging ability remains unclear. Using DFT and TD-DFT methods, we systematically investigated how electron withdrawing (-CN) and electron donating (−NH2) groups, together with dichloromethane and dimethyl sulfoxide solvents, regulate ESIPT and antioxidant activity. The -CN group promotes ESIPT but weakens antioxidant activity, whereas -NH2 shows the opposite effect. Lower solvent polarity favors ESIPT. These findings provide theoretical guidance for designing phenolic antioxidants and functionalized ligands.
{"title":"Effects of substituents and solvent polarity on ESIPT and antioxidant activity of 2,6-Dihydroxybenzaldehyde","authors":"Haoran Ma , Yongchun Li , Nan Yang , Siyi Wang , Xiatiguli Kahaer , Mei Xiang , Bumaliya Abulimiti , Xiaoning Wang","doi":"10.1016/j.cplett.2026.142681","DOIUrl":"10.1016/j.cplett.2026.142681","url":null,"abstract":"<div><div>2,6-Dihydroxybenzaldehyde (2,6-DHBA), featuring ortho phenolic hydroxyl groups, exhibits notable antioxidant properties. However, the influence of substituents and solvent polarity on its ESIPT behavior and radical scavenging ability remains unclear. Using DFT and TD-DFT methods, we systematically investigated how electron withdrawing (-CN) and electron donating (−NH<sub>2</sub>) groups, together with dichloromethane and dimethyl sulfoxide solvents, regulate ESIPT and antioxidant activity. The -CN group promotes ESIPT but weakens antioxidant activity, whereas -NH<sub>2</sub> shows the opposite effect. Lower solvent polarity favors ESIPT. These findings provide theoretical guidance for designing phenolic antioxidants and functionalized ligands.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"887 ","pages":"Article 142681"},"PeriodicalIF":3.1,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074909","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}
Pub Date : 2026-01-24DOI: 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.
{"title":"Perfect spin-filtering effect and multifunctional spin logic gates in planar four-coordinate Fe complexes-based molecular device","authors":"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)","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":"2026-01-24","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}
Pub Date : 2026-01-24DOI: 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 (RCSπ) 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 RCSπ, whereas total NICS is distorted by the other contributions, highlighting RCSπ 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。
{"title":"Revisiting aromaticity of five-membered rings: a dissected ring current analysis","authors":"Rodrigo Báez-Grez , 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> > 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)<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":"2026-01-24","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}
Pub Date : 2026-01-24DOI: 10.1016/j.cplett.2026.142678
Zachary T. Mentzer, Harris E. Brotman, Mehdi B. Zanjani
Finite-sized biological or synthetic assemblies comprise discrete sets of constituent building blocks, resulting in size-dependent structural and functional properties. While these systems offer promising applications, controlling their properties remains challenging through the high-dimensional, combinatorial nature of the design space, necessitating extensive experimental exploration. Here, we develop an attention-based machine learning framework to predict structural properties of microscale finite-sized assemblies by discretization into tokenized sequences. The model accurately predicts system properties, bypassing the need to individually evaluate building block combinations. This approach provides a foundation for the inverse design of assemblies with desired geometries and tunable properties.
{"title":"Predicting geometrical features of finite-sized colloidal assemblies using attention-based learning","authors":"Zachary T. Mentzer, Harris E. Brotman, Mehdi B. Zanjani","doi":"10.1016/j.cplett.2026.142678","DOIUrl":"10.1016/j.cplett.2026.142678","url":null,"abstract":"<div><div>Finite-sized biological or synthetic assemblies comprise discrete sets of constituent building blocks, resulting in size-dependent structural and functional properties. While these systems offer promising applications, controlling their properties remains challenging through the high-dimensional, combinatorial nature of the design space, necessitating extensive experimental exploration. Here, we develop an attention-based machine learning framework to predict structural properties of microscale finite-sized assemblies by discretization into tokenized sequences. The model accurately predicts system properties, bypassing the need to individually evaluate building block combinations. This approach provides a foundation for the inverse design of assemblies with desired geometries and tunable properties.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"887 ","pages":"Article 142678"},"PeriodicalIF":3.1,"publicationDate":"2026-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074888","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}
Pub Date : 2026-01-23DOI: 10.1016/j.cplett.2026.142679
Fang Liu , Xiangyi Luo , Ye Wang , Jiahe Chen
Inspired by its potential probe application of fungi and targeted antimicrobial, DPNAP is explored about its photo-induced properties and ESIPT mechanism associated with surrounding polarities. Given the significance of solvent surroundings, the potential solvent-polarity-regulated photo-induced behaviors and ESIPT behaviors are mainly focused. Choosing three representative solvents, we find dual hydrogen bonds of DPNAP fluorophore could be largely strengthening in polar solvent environments. By constructing potential energy surface (PES) and searching reaction transition state (TS) geometries, the solvent-polarity-associated single ESIPT mechanism could be confirmed (just along with O1-H2···N3 hydrogen bond), even though double hydrogen bonds DPNAP fluorophore owns.
{"title":"Solvent-polarity-associated hydrogen bonding interactions and ESIPT behaviors for DPNAP fluorophore: A theoretical investigation","authors":"Fang Liu , Xiangyi Luo , Ye Wang , Jiahe Chen","doi":"10.1016/j.cplett.2026.142679","DOIUrl":"10.1016/j.cplett.2026.142679","url":null,"abstract":"<div><div>Inspired by its potential probe application of fungi and targeted antimicrobial, DPNAP is explored about its photo-induced properties and ESIPT mechanism associated with surrounding polarities. Given the significance of solvent surroundings, the potential solvent-polarity-regulated photo-induced behaviors and ESIPT behaviors are mainly focused. Choosing three representative solvents, we find dual hydrogen bonds of DPNAP fluorophore could be largely strengthening in polar solvent environments. By constructing potential energy surface (PES) and searching reaction transition state (TS) geometries, the solvent-polarity-associated single ESIPT mechanism could be confirmed (just along with O1-H2···N3 hydrogen bond), even though double hydrogen bonds DPNAP fluorophore owns.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"887 ","pages":"Article 142679"},"PeriodicalIF":3.1,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074912","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}
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