Chemphyschem最新文献_第4页

Integrating Low-Cost xTB Electronic Priors for Predicting Electronic and Excited-State Properties of Organic Conjugated Molecules 集成低成本xTB电子先验预测有机共轭分子的电子和激发态性质。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-09-08 DOI: 10.1002/cphc.70562

Min Zeng, Lian Huai, Tong Liu, Yuyu Liu, Xingqun Jiang

{"title":"Integrating Low-Cost xTB Electronic Priors for Predicting Electronic and Excited-State Properties of Organic Conjugated Molecules","authors":"Min Zeng, Lian Huai, Tong Liu, Yuyu Liu, Xingqun Jiang","doi":"10.1002/cphc.70562","DOIUrl":"10.1002/cphc.70562","url":null,"abstract":"Accurate prediction of electronic and excited-state properties is important for the computational screening of organic conjugated molecules. However, this task remains challenging because these properties depend on both local chemical environments and global structural and electronic information. In this work, we develop a dual-tower molecular representation framework that combines a graph tower for local atom–bond connectivity with a global tower for global structural information and extended tight-binding (xTB)-derived electronic priors. Evaluated on the OCELOT chromophore dataset, the fusion of graph representations with global structural features consistently outperforms the graph-only baseline. Incorporating xTB descriptors into the global tower further reduces the average MAE. The best fusion model reaches an average MAE of 0.148 ± 0.001 eV compared with 0.156 ± 0.002 eV for the graph-only model. Ablation studies across different fusion strategies show that the main benefit arises from combining local atom–bond connectivity information with global molecule-level information rather than from any single fusion operator. These results demonstrate that global representations combining RDKit descriptors, Morgan fingerprints, and xTB-derived electronic descriptors provide useful support for graph neural networks (GNNs) to predict electronic and excited-state properties of organic conjugated molecules.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 17","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148910888","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

Orbital Engineering of π–d Conjugation in One-Dimensional Metal–Organic Materials for Lithium-Ion Batteries: A DFT Study 锂离子电池用一维金属-有机材料π-d共轭的轨道工程：DFT研究

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-09-08 DOI: 10.1002/cphc.70560

Mingli Li, Di Zhao, Lei Zhang, Pan Yang, Feixue Han, Zhenzhen Wu, Shanqing Zhang, Yun Wang

{"title":"Orbital Engineering of π–d Conjugation in One-Dimensional Metal–Organic Materials for Lithium-Ion Batteries: A DFT Study","authors":"Mingli Li, Di Zhao, Lei Zhang, Pan Yang, Feixue Han, Zhenzhen Wu, Shanqing Zhang, Yun Wang","doi":"10.1002/cphc.70560","DOIUrl":"10.1002/cphc.70560","url":null,"abstract":"Understanding and tuning π–d conjugation is essential for advancing metal–organic materials in metal-ion batteries. Here, we applied density functional theory (DFT) to systematically investigate π–d conjugation in metal–organic systems. Using a Ni-based metal–organic polymer as the model system, our results show that strong π–d conjugation originates from effective hybridization between Ni 3d orbitals and ligand π orbitals mediated by bridging groups. Among the three bridging groups (─O, ─S, and ─NH), S provides the strongest coupling due to favorable orbital overlap. Ligand functionalization further modulates this interaction via energy level alignment, where electron-withdrawing groups enhance π–d hybridization and charge delocalization, while electron-donating groups weaken it. These factors collectively influence Li adsorption and electrochemical performance. This study establishes a unified design strategy combining bridge atom selection and functional group tuning to optimize π–d conjugation for high- performance metal–organic electrode materials.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 17","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13553211/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148910843","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

CO2 Activation by Small Copper, Cobalt, and Yttrium Oxide Clusters Probed via Infrared Multiple-Photon Dissociation Spectroscopy 通过红外多光子解离光谱探测小铜，钴和钇氧化物簇对CO2的活化。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-09-07 DOI: 10.1002/cphc.70559

Pavol Mikolaj, Joost M. Bakker, Sandra M. Lang

{"title":"CO2 Activation by Small Copper, Cobalt, and Yttrium Oxide Clusters Probed via Infrared Multiple-Photon Dissociation Spectroscopy","authors":"Pavol Mikolaj, Joost M. Bakker, Sandra M. Lang","doi":"10.1002/cphc.70559","DOIUrl":"10.1002/cphc.70559","url":null,"abstract":"The interaction of CO2 with Cu, Co, and Y oxide clusters of different size, composition, and charge is investigated via infrared multiple-photon dissociation (IR-MPD) spectroscopy. The IR-MPD spectra of MxOy(CO2)+/− (M = Cu, Co, Y) complexes reveal the non-activated binding of CO2 to all cationic clusters. In contrast, CO2 is activated by all anions via formation of carbonate-like CO3 units. Density functional theory(DFT) calculations on M2O2+/− model systems suggest that for CO2 activation in general, the energy difference between the cluster highest occupied molecular orbital (HOMO) and the CO2 lowest unoccupied molecular orbital (LUMO) is crucial. The binding motif of the activated CO2 molecule, however, depends on a fine interplay between the nature of the orbitals close to the HOMO and the oxidation state of the metal atoms. CO3 formation is favored when the cluster HOMO or any energetically close lying molecular orbital (MO) is at least partially localized on one of the cluster oxygen atoms. In contrast, if such MOs are energetically less favorable, η2-(C,O) and η2-(O,O) binding to one of the metal atoms can be favored, provided the already positively charged metal atom can transfer electron density, i.e., adopt an even higher oxidation state.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 17","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13549768/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148905217","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Aerogen Bonding in NgO2F2 (Ng = Xe, Kr): A Computational Study NgO2F2 （Ng = Xe, Kr）中气相键合的计算研究

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-09-06 DOI: 10.1002/cphc.70551

Zeel Y. Surati, Jyoti Sharma, Soumya R. Dash, Kumar Vanka

{"title":"Aerogen Bonding in NgO2F2 (Ng = Xe, Kr): A Computational Study","authors":"Zeel Y. Surati, Jyoti Sharma, Soumya R. Dash, Kumar Vanka","doi":"10.1002/cphc.70551","DOIUrl":"10.1002/cphc.70551","url":null,"abstract":"Aerogen bonding in NgO2F2 (Ng = Xe, Kr) was investigated using quantum chemical calculations with O-, N-, and C-donor nucleophiles. Molecular electrostatic potential analysis reveals two σ-hole regions along the extensions of the Ng─O bonds, making NgO2F2 closer to XeO3, but with two binding sites and no distinct π-hole regions as in XeOF2. All nucleophiles form stable 1:1 and 1:2 adducts, with conventional O- and N-donor lewis bases giving moderate stabilization, while the carbene donors 5-NHC, cAAC, and aNHC bind much more strongly. Structural, atoms-in-molecules (AIM), noncovalent interaction (NCI), natural bond orbital (NBO), and energy decomposition (EDA) analyses show that the stronger carbene adducts arise from shorter Ng…C interactions, larger WBI and BCP values, and enhanced LP(C) → BD*(Ng─O) donation. Minor orientation-dependent LP(donor) → BD*(Ng─F) contributions are also observed in selected adducts. The interactions remain primarily electrostatic, with significant orbital contribution, especially for the carbene adducts. Secondary C─H…O/F interactions, together with smaller but non-negligible back-donation from the lone pairs of Ng, provide additional stabilization to the adducts.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 17","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148900303","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

Electrochemical Determination of the Ionization Energy and the Electron Affinity of Lead Halide Perovskite Thin Films: A Comparison to Ultraviolet Photoelectron Spectroscopy 卤化铅钙钛矿薄膜电离能和电子亲和力的电化学测定：与紫外光电子能谱的比较。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-09-05 DOI: 10.1002/cphc.70478

Katarina Gugujonovic, Rene Zahrhuber, Thorsten Wagner, Felix Mayr, Elisabeth Leeb, Munise Cobet, Niyazi Serdar Sariciftci, Markus Clark Scharber

{"title":"Electrochemical Determination of the Ionization Energy and the Electron Affinity of Lead Halide Perovskite Thin Films: A Comparison to Ultraviolet Photoelectron Spectroscopy","authors":"Katarina Gugujonovic, Rene Zahrhuber, Thorsten Wagner, Felix Mayr, Elisabeth Leeb, Munise Cobet, Niyazi Serdar Sariciftci, Markus Clark Scharber","doi":"10.1002/cphc.70478","DOIUrl":"10.1002/cphc.70478","url":null,"abstract":"Reliable determination of ionization energies (IE) and electron affinities (EA) is essential for understanding energy-level alignment in solar cells. Here, we benchmark cyclic voltammetry (CV) and electrochemical voltage spectroscopy (EVS) for IE and EA determination against ultraviolet photoelectron spectroscopy (UPS) for IE and the combination of UPS and photothermal deflection spectroscopy (PDS) for EA. The investigated materials are <math></math> perovskite thin films with varying bromide fraction y = 0–1. Onset potentials and energies were reproducibly extracted using tangent-based scripts, avoiding data smoothing and minimizing user bias. The optical band gap scales linearly with bromide fraction. The IE remains approximately constant up to y = 0.4 (EVS) and y = 0.6 (CV), increasing upon further substitution. All investigated methods consistently reveal a decrease in EA with increasing bromide content. Finally, we highlight practical considerations relevant to the application of EC methods and UPS.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 17","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13546371/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148896591","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Vibrational Spectra, Conformations, and Optical Rotation of Aqueous Amino Acids: Zwitterions of L-Alanine and L-Valine 氨基酸的振动光谱、构象和旋光度：l -丙氨酸和l -缬氨酸的两性离子。

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-09-03 DOI: 10.1002/cphc.70536

Sergey A. Katsyuba, Timur I. Burganov, Tatiana P. Gerasimova, Thomas Froitzheim, Stefan Grimme

{"title":"Vibrational Spectra, Conformations, and Optical Rotation of Aqueous Amino Acids: Zwitterions of L-Alanine and L-Valine","authors":"Sergey A. Katsyuba, Timur I. Burganov, Tatiana P. Gerasimova, Thomas Froitzheim, Stefan Grimme","doi":"10.1002/cphc.70536","DOIUrl":"10.1002/cphc.70536","url":null,"abstract":"We demonstrate that an efficient computational protocol for accurate quantum mechanical (QM) modeling of IR and Raman spectra of condensed-phase systems is applicable to aqueous zwitterions of L-alanine and L-valine. The approach is based on generating energetically low-lying cluster structures consisting of the solute surrounded by an explicit solvation shell, optimized at the DFT level. Such cluster models are shown to reliably reproduce experimental vibrational frequencies and relative IR and Raman intensities of both amino acids at the B3LYP-D3/def2-TZVP level, provided that 25 water molecules are included. The accuracy of the simulations is sufficient to resolve all three conformers of valine and to identify their spectroscopic signatures. Relative conformer populations are estimated from the experimental intensities of the corresponding conformational marker bands, and conformationally averaged optical rotations (OR) of valine are computed using several QM protocols for [α]D. A comparative analysis of the full set of computed OR values for both amino acids yields an intrinsic margin of error in TDDFT calculations of [α]D of approximately 50° cm3/(g dm).","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 17","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148886409","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

MoCoC− Bimetallic Anion Mediates Room-Temperature Conversion of Four NH3 to Five H2 Molecules MoCoC−双金属阴离子介导4个NH3分子室温转化为5个H2分子

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-09-01 DOI: 10.1002/cphc.70556

Lei-Ting Zhang, Feng-Xiang Zhang, Yong-Qi Ding, Jia-Bi Ma

{"title":"MoCoC− Bimetallic Anion Mediates Room-Temperature Conversion of Four NH3 to Five H2 Molecules","authors":"Lei-Ting Zhang, Feng-Xiang Zhang, Yong-Qi Ding, Jia-Bi Ma","doi":"10.1002/cphc.70556","DOIUrl":"https://doi.org/10.1002/cphc.70556","url":null,"abstract":"Ammonia (NH3) decomposition is critical for a zero-carbon hydrogen economy. While gas-phase transition metal cations have been extensively studied as ideal model systems, the reactivity of anions remains largely unexplored. Herein, we report that the heteronuclear metal anion MoCoC− exhibits exceptional reactivity, sequentially activating four NH3 molecules and releasing five H2 molecules. The first two NH3 molecules are completely decomposed, releasing all six hydrogen atoms as three H2 to form MoCoCN2−. The third and fourth NH3 molecules each release one additional H2, yielding the final product MoCoCN2(NH)2−. Density functional theory calculations were employed to elucidate the decomposition mechanisms of the first two NH3 molecules. In the first step, which generates H2 and MoCoCNH−, bond state switching between Mo and Co facilitates the activation of H atoms in NH3, while the C atom in the cluster provides additional electron density. In the subsequent reaction with the second NH3 molecule, two H2 molecules are released, leading to MoCoCN2−. In this step, Mo and Co act as hydrogen shuttles and electron donors for N─H bond activation. This study on MoCo-based anions for NH3 decomposition provides a theoretical foundation for elucidating the mechanism of condensed-phase MoCo catalysts in NH3 decomposition.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 17","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148860080","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

Polarized ATR-FTIR Spectroscopy Reveals Light-Induced Peptide Insertion of LAH4 Into Photoswitchable Membranes 极化ATR-FTIR光谱揭示光诱导肽插入到光开关膜

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-31 DOI: 10.1002/cphc.70554

Celine Eckert, Selina Mertens, Karin Hauser

{"title":"Polarized ATR-FTIR Spectroscopy Reveals Light-Induced Peptide Insertion of LAH4 Into Photoswitchable Membranes","authors":"Celine Eckert, Selina Mertens, Karin Hauser","doi":"10.1002/cphc.70554","DOIUrl":"https://doi.org/10.1002/cphc.70554","url":null,"abstract":"Photoswitchable biomimetic membranes can be controlled by light and offer the possibility to study the role of membrane dynamics for the interaction with antimicrobial peptides. The α-helical peptide LAH4, a well-studied model system, interacts with membranes in a pH-dependent manner. It binds to the membrane surface at acidic pH and inserts into the membrane at basic pH conditions. Polarized attenuated total reflection (ATR) Fourier-transform infrared (FTIR) spectroscopy was employed to probe peptide orientation and structural changes, with particular emphasis on the pH-dependent response of LAH4 to light-induced membrane perturbations. Photoswitchable azoPC lipids were incorporated in large unilamellar vesicles (LUVs) as well as in DIBMA-stabilized nanodiscs, and the light-induced cis-to-trans isomerization of the azobenzene was monitored by characteristic vibrational modes showing a reversible transition between two membrane states for both membrane systems. The measurements reveal that photoswitching between the membrane states induces the reorientation of the surface-bound peptide toward a membrane-inserted state. The findings underline the potential of photoswitchable membranes for the study of lipid-peptide interactions as well as the importance of membrane dynamics for antimicrobial activity.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 17","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.70554","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148860123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Characterization and Theoretical Insights Into Coumarin-Based Sensitizers for Dye-Sensitized Solar Cells 染料敏化太阳能电池香豆素基敏化剂的表征和理论见解

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-31 DOI: 10.1002/cphc.70546

Aman Kumar, Anamika Chaudhari, Sudhanshu Kumar, Bhawana Tripathi, Sudip Mandal, Suman Kushwaha

引用次数: 0

Predicting Activation Barriers With Ring and Bond Critical Points in the Kemp Elimination Reaction 用Kemp消除反应中的环和键临界点预测激活势垒

IF 2.4 3区化学

Chemphyschem Pub Date : 2026-08-31 DOI: 10.1002/cphc.70555

Hunter Redmon, Katie H. Ly, James Mulcahey, Amanda Morgenstern

{"title":"Predicting Activation Barriers With Ring and Bond Critical Points in the Kemp Elimination Reaction","authors":"Hunter Redmon, Katie H. Ly, James Mulcahey, Amanda Morgenstern","doi":"10.1002/cphc.70555","DOIUrl":"https://doi.org/10.1002/cphc.70555","url":null,"abstract":"The Kemp elimination reaction can be catalyzed by computationally designed enzymes. After undergoing directed evolution, changes to the positioning of active site residues in Kemp eliminases can alter electric fields (EFs) and improve catalytic efficiency. However, optimizing EFs during the enzyme design process remains a challenge. Here we investigate how implicit solvation and external EFs reposition bond and ring critical points (CPs) in the reactant state of a truncated Kemp eliminase system using density functional theory and the quantum theory of atoms in molecules. We find that a linear correlation exists between the bond-ring CP distances integral to the Kemp elimination ring-opening reaction and activation barriers. The N─O stretching mode of the benzisoxazole ring that coincides with the reaction coordinate is also found to move ring CPs to varying degrees for each EF strength tested. EFs that move the ring CPs the largest magnitude and in the proper orientation toward the N─O bond CP correlate with the smallest activation barriers. Since reactant state QTAIM calculations are significantly less expensive than directly calculating activation barriers, this may provide an avenue for screening computationally designed enzymes that catalyze ring-opening reactions.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"27 17","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148860118","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