Chemphyschem最新文献_第8页

Structure and Optical Properties of Alkali-Metal Ion (Li+, Na+, K+, Rb+, and Cs+) Endohedral Cyclo[18]carbon 碱金属离子（Li+, Na+, K+, Rb+, Cs+）内嵌环[18]碳的结构与光学性质

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-07 DOI: 10.1002/cphc.202500009

Yang Xiao, Xia Wang, Xiufen Yan, Zeyu Liu, Mengdi Zhao, Tian Lu

{"title":"Structure and Optical Properties of Alkali-Metal Ion (Li+, Na+, K+, Rb+, and Cs+) Endohedral Cyclo[18]carbon","authors":"Yang Xiao, Xia Wang, Xiufen Yan, Zeyu Liu, Mengdi Zhao, Tian Lu","doi":"10.1002/cphc.202500009","DOIUrl":"10.1002/cphc.202500009","url":null,"abstract":"With growing interest in carbon-based materials for energy storage and active research in the field of advanced optoelectronic devices, ten complexes are designed with cyclo[18]carbon (C18) inside and outside complexing alkali metal ion (M+ = Li+, Na+, K+, Rb+, and Cs+), respectively, referred to as M+@C18in and M+@C18out, and careful analysis of their structure, binding interaction between M+ and C18, as well as optical properties of stable endohedral complexes M+@C18in is performed. The effects of atomic number of alkali metals on structure, binding interaction, electronic absorption spectrum, and molecular (hyper)polarizability of the M+@C18in are studied using accurate (time-dependent) density functional theory calculations. The research suggests that the binding modes and strengths of different M+ with C18 are different but there is no evident difference in electronic absorption spectra of the complexes. The polarizability and second hyperpolarizability of M+@C18in containing different alkali-metal ions are close due to the similarity of ionic properties but their first hyperpolarizability differs greatly by reason of discrepancy in molecular symmetry. The similarities and differences in structure, fragment interaction, electronic absorption spectrum, and (hyper)polarizability of M+@C18in are explored using advanced wavefunction analysis methods.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 11","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794785","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

Spin-Crossover in a Dinuclear Iron(II) Complex on Highly Oriented Pyrolytic Graphite: An X-Ray Absorption Spectroscopy Study. HOPG上双核铁（II）配合物的自旋交叉：x射线吸收光谱研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-07 DOI: 10.1002/cphc.202401081

Marcel Walter, Sebastien Elie Hadjadj, Clara Trommer, Jorge Torres, Jendrik Gördes, David Swerev, Tauqir Shinwari, Christian Lotze, Chen Luo, Florin Radu, Felix Tuczek, Sangeeta Thakur, Wolfgang Kuch

{"title":"Spin-Crossover in a Dinuclear Iron(II) Complex on Highly Oriented Pyrolytic Graphite: An X-Ray Absorption Spectroscopy Study.","authors":"Marcel Walter, Sebastien Elie Hadjadj, Clara Trommer, Jorge Torres, Jendrik Gördes, David Swerev, Tauqir Shinwari, Christian Lotze, Chen Luo, Florin Radu, Felix Tuczek, Sangeeta Thakur, Wolfgang Kuch","doi":"10.1002/cphc.202401081","DOIUrl":"10.1002/cphc.202401081","url":null,"abstract":"The spin-crossover (SCO) properties of the dinuclear complex <math> <semantics><mrow><mo>[</mo> <msub><mrow><mo>{</mo> <mtext>Fe</mtext> <msub> <mrow><mrow><mo>(</mo> <msub><mi>H</mi> <mn>2</mn></msub> <mi>B</mi> <msub><mrow><mo>(</mo> <mtext>pz</mtext> <mo>)</mo></mrow> <mn>2</mn></msub> <mo>)</mo></mrow> </mrow> <mn>2</mn></msub> <mo>}</mo></mrow> <mn>2</mn></msub> <mi>μ</mi> <mo>-</mo> <mo>(</mo> <msub><mrow><mtext>ac(bipy)</mtext></mrow> <mn>2</mn></msub> <mo>)</mo> <mo>]</mo></mrow> <annotation>$left[right. left{right. text{Fe} left(left(right. left(text{H}right)_{2} text{B} left(left(right. text{pz} left.right)right)_{2} left.right)right)_{2} left(left.right}right)_{2} mu - left(right. left(text{ac(bipy)}right)_{2} left.right) left]right.$</annotation></semantics> </math> are studied as (sub)-monolayer and thin film deposited by an ultrahigh vacuum liquid-jet deposition technique on highly oriented pyrolytic graphite (HOPG) by X-ray absorption spectroscopy. A comparison of the SCO properties of thin films and a dropcast sample indicates that the spin-switching probability of the thin films is limited due to substrate-molecule interactions. The maximum percentage of molecules in the low-spin (LS) state observed for 0.7 and 1.8 monolayers (ML) is ≈43% at a temperature of 80 K in comparison to the dropcast sample where ≈66% of the complex is in the LS state. The similar switching properties of the dropcast sample as of a bulk powder sample confirm that the SCO properties are not affected by the presence of solvent necessary for deposition. The soft-X-ray-induced excited spin-state trapping (SOXIESST) effect is pronounced in all samples, although the light-induced high-spin (HS) fraction of the dropcast and the thin-film samples on HOPG is higher as compared to the HS fraction attained by SOXIESST, which confirms the sensitivity of the complex to light.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e2401081"},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794753","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

Unfolding of the Villin Headpiece Domain: Revealing Structural Heterogeneity with Time-Resolved X-Ray Solution Scattering and Markov State Modeling Villin头饰域的展开：用时间分辨x射线溶液散射和马尔可夫态模型揭示结构非均质性。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-07 DOI: 10.1002/cphc.202500049

Adam K. Nijhawan, Arnold M. Chan, Madeline B. Ho, Changmin Lee, Irina Kosheleva, Lin X. Chen, Kevin L. Kohlstedt

{"title":"Unfolding of the Villin Headpiece Domain: Revealing Structural Heterogeneity with Time-Resolved X-Ray Solution Scattering and Markov State Modeling","authors":"Adam K. Nijhawan, Arnold M. Chan, Madeline B. Ho, Changmin Lee, Irina Kosheleva, Lin X. Chen, Kevin L. Kohlstedt","doi":"10.1002/cphc.202500049","DOIUrl":"10.1002/cphc.202500049","url":null,"abstract":"Understanding protein folding pathways is crucial to deciphering the principles of protein structure and function. Here, the unfolding dynamics of the 35-residue villin headpiece (HP35) and a norleucine-substituted variant (2F4K) using a combination of experimental and computational techniques is investigated. Time-resolved X-ray solution scattering coupled with equilibrium molecular dynamics simulations and Markov state modeling reveals distinct unfolding mechanisms between the two variants: HP35 and 2F4K. Specifically, HP35 exhibits a two-state unfolding process, whereas an intermediate state is identified for the 2F4K mutant. A Markov state model constructed from simulations is used to map atomic-level transitions to experimental observations, providing insights into the role of sequence variations in modulating folding pathways. The findings underscore the importance of integrating experimental and computational approaches to unravel protein unfolding mechanisms between heterogenous structural ensembles.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202500049","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794823","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

Reactions of 1,4-Diborinine Derivatives with CO2 1,4-二硼碱衍生物与CO2的反应。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-03 DOI: 10.1002/cphc.202401049

Maxime Ferrer, Ibon Alkorta, José Elguero, Israel Fernández

引用次数: 0

QTAIM Analysis of a [2]Rotaxane Molecular Shuttle with a 2,2′-Bipyridyl Rigid Core 具有2,2'-联吡啶刚性核的[2]轮烷分子梭的QTAIM分析。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-03 DOI: 10.1002/cphc.202500074

Costantino Zazza, Nico Sanna, Stefano Borocci, Felice Grandinetti

{"title":"QTAIM Analysis of a [2]Rotaxane Molecular Shuttle with a 2,2′-Bipyridyl Rigid Core","authors":"Costantino Zazza, Nico Sanna, Stefano Borocci, Felice Grandinetti","doi":"10.1002/cphc.202500074","DOIUrl":"10.1002/cphc.202500074","url":null,"abstract":"Chemical contacts responsible for the supramolecular assembly of a rigid H-shaped [2]rotaxane molecular shuttle composed of a 24-crown-8(24C8) macrocycle on a molecular thread containing two benzimidazole (Bzi) recognition sites and a central 2,2′-bipyridyl (Bipy) rigid core are analytically addressed by combining the Quantum Theory of Atoms in Molecules (QTAIM) with density functional theory (DFT). In this respect, the available crystallographic structure—CCDC number 2248267—is taken as a reference condition for addressing the nature of the chemical interactions finely modulating the shuttling of the 24C8 between Bzi stations. Moreover, previous DFT computations (Chem. Sci., 2023, 14, 7215) are extended over a supercomputing environment to address the proposed ligand exchange mechanism involving DMF solvent molecules and promoting the observed shuttling process upon the addition of Zn(II) cations. To this end, converged DFT wavefunctions are fully analyzed by means of electron density ρ(r) and local electronic energy density—H(r)—descriptors; interestingly, the derived covalent versus noncovalent interaction patterns shed some light on the mutual position of the macrocycle along the axle following the coordination of Zn(II) ions in DMF solvent.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202500074","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143771475","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

Nonadditive CO2 Uptake of Type II Porous Liquids Based on Imine Cages 基于亚胺笼的II型多孔液体的非添加剂CO2吸收。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-03 DOI: 10.1002/cphc.202400985

Lu Lu, Chao-Wen Chang, Stephen Schuyten, Ankana Roy, David S. Sholl, Ryan P. Lively

{"title":"Nonadditive CO2 Uptake of Type II Porous Liquids Based on Imine Cages","authors":"Lu Lu, Chao-Wen Chang, Stephen Schuyten, Ankana Roy, David S. Sholl, Ryan P. Lively","doi":"10.1002/cphc.202400985","DOIUrl":"10.1002/cphc.202400985","url":null,"abstract":"Type II porous liquids can potentially exploit the fluidity of liquids and sorption properties of porous sorbents, yet CO2 uptake in porous liquids is still poorly understood. Molecular simulations and experiments are used to examine CO2 uptake by a prototypical porous liquid composed of porous organic cages (CC13) in 2′-hydroxyacetophenone (2′-HAP). The simulations are in reasonable agreement with experimental measurements of CO2 solubility and provide unambiguous information on the partitioning of CO2 within microenvironments in the liquid. Analysis of CO2 dynamics is performed using these simulations, including assessing the self-diffusivity of CO2 in both the neat solvent and porous liquid. This offers insights into the kinetics of CO2 uptake and transport in type II porous liquids based on imine cages. Experiments with type II porous liquids formed by dissolving CC13 in three different size-excluded solvents show nonadditive CO2 absorption relative to predictions based on ideal volume additivity. This nonadditive absorption behavior is also observed in simulations. Nonadditive CO2 uptake is also demonstrated in type II porous liquids based on another imine-based porous cage, CC19.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202400985","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143779230","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

Overcoming Challenges in Density Functional Theory-Based Calculations of Hyperfine Coupling Constants for Heavy Heteroatom Radicals 克服基于dft计算重杂原子自由基超精细耦合常数的挑战。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-03 DOI: 10.1002/cphc.202400978

Maciej Witwicki

{"title":"Overcoming Challenges in Density Functional Theory-Based Calculations of Hyperfine Coupling Constants for Heavy Heteroatom Radicals","authors":"Maciej Witwicki","doi":"10.1002/cphc.202400978","DOIUrl":"10.1002/cphc.202400978","url":null,"abstract":"This study assesses density functional theory (DFT) methods for their accuracy in calculating hyperfine coupling constants (HFCCs) of heavy heteroatom radicals with heteroatoms including Sb, Bi, In, Tl, and Sn. Given the essential role of electron paramagnetic resonance spectroscopy in characterization of these species, it is crucial that theoretical models can predict HFCCs accurately for heavy elements. This work presents a computational approach that addresses crucial factors: selection of basis set, hybrid exchange-correlation functional, higher Hartree–Fock (HF) exchange, and the Gaussian description of nuclear charge. The relativistic effects are introduced using one-component linear response theory with the second-order Douglas–Kroll–Hess formalism and the fully relativistic four-component Dirac–Kohn–Sham method. The findings show that, while one-component DFT is accurate for the 4th-row elements, the four-component method is more precise for the 5th-row radicals and the one-component approach fails for the 6th-row congeners. Increasing HF exchange significantly improves HFCC predictions. The developed framework for accurate HFCC calculations will enhance the understanding of electronic and magnetic properties of heavy element radicals and can be used by computational chemists and experimentalists alike.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 10","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143771474","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

Front Cover: Revealing Mechanisms of Lithium-Mediated Nitrogen Reduction Reaction from First-Principles Simulations (ChemPhysChem 7/2025) 封面：从第一线原理模拟揭示锂介导的氮还原反应机制（chemphysichem 7/2025）

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-02 DOI: 10.1002/cphc.202580701

Chengyu Zhou, Qing Zhao

引用次数: 0

Cover Feature: Deciphering Mg-Surface Interactions with Unsaturated Hydrocarbons: An Integrated Experimental-Theoretical Study (ChemPhysChem 7/2025) 封面专题：破译mg -表面与不饱和烃的相互作用：一个综合的实验-理论研究（chemphysichem 7/2025）

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-04-02 DOI: 10.1002/cphc.202580702

Sourav Ghoshal, Nathaniel Carnegie, Chidozie Ezeakunne, Beni B. Dangi, Shyam Kattel

引用次数: 0

First-Principles Investigation of 2D o-Al2C2 Monolayer: A High-Performance Anode for Li/Na–Ion Batteries 二维o-Al2C2单层：高性能锂/钠离子电池负极的第一性原理研究。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-03-28 DOI: 10.1002/cphc.202500025

Mohamed Agouri, Ayoub Benaddi, Nabil Khossossi, Said El Filali, Abderrahman Abbassi, Abdellatif Hasnaoui, Souad Taj, Bouzid Manaut

{"title":"First-Principles Investigation of 2D o-Al2C2 Monolayer: A High-Performance Anode for Li/Na–Ion Batteries","authors":"Mohamed Agouri, Ayoub Benaddi, Nabil Khossossi, Said El Filali, Abderrahman Abbassi, Abdellatif Hasnaoui, Souad Taj, Bouzid Manaut","doi":"10.1002/cphc.202500025","DOIUrl":"10.1002/cphc.202500025","url":null,"abstract":"The development of novel anode materials with superior electrochemical performance is imperative for advancing next-generation high-performance rechargeable batteries beyond current limitations. In this study, it presents a 2D o-Al2C2 monolayer as a promising lightweight candidate for lithium and sodium–ion battery systems, based on the density functional theory investigations and ab initio molecular dynamics (AIMD) simulations. Our comprehensive investigation demonstrates that the o-Al2C2 monolayer exhibits remarkable stability with a cohesive energy of −5.30 eV atom−1 and maintains its structural integrity at room temperature during extended AIMD simulations. The o-Al2C2 monolayer demonstrates exceptional electrochemical characteristics for Li and Na storage: theoretical specific capacities of 3780.42 and 3436.75 mA h g−1, optimal average open circuit voltages of 0.81 and 0.67 V, and favorable diffusion barriers of 0.62 eV and 0.31 eV, respectively. These performance metrics significantly surpass those of conventional graphite (372 mA h g−1) and other recently reported 2D anode materials, establishing o-Al2C2 as an exceptionally promising candidate for next-generation energy storage applications. Hence, this current theoretical investigation suggests that the o-Al2C2 monolayer holds significant potential for future experimental studies in lithium and sodium storage applications for LIB and NIB systems.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 12","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143729067","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