Chemphyschem最新文献_第2页

QTAIM analysis of a [2]rotaxane molecular shuttle with a 2,2'-bipyridyl rigid core.

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":"https://doi.org/10.1002/cphc.202500074","url":null,"abstract":"Chemical contacts responsible for the supramolecular assembly of a rigid H-shaped [2]rotaxane molecular shuttle composed by 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 combining 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 vs non-covalent 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":" ","pages":"e202500074"},"PeriodicalIF":2.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Non-additive CO2 uptake of Type II porous liquids base on imine cages.

IF 2.3 3区化学

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

L U Lu, Chao-Wen Chang, Stephen Schuyten, Ankana Roy, David S Sholl, Ryan Lively

{"title":"Non-additive CO2 uptake of Type II porous liquids base on imine cages.","authors":"L U Lu, Chao-Wen Chang, Stephen Schuyten, Ankana Roy, David S Sholl, Ryan Lively","doi":"10.1002/cphc.202400985","DOIUrl":"https://doi.org/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. We used molecular simulations and experiments to examine CO2 uptake by a prototypical porous liquid composed of porous organic cages (CC13) in 2'-hydroxyacetophenone (2'-HAP). Our 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 was 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 showed non-additive CO2 absorption relative to predictions based on ideal volume additivity. This non-additive absorption behavior was also observed in simulations. We also demonstrated non-additive CO2 uptake from Type II porous liquids based on another imine-based porous cage, CC19.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400985"},"PeriodicalIF":2.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Overcoming Challenges in DFT-Based Calculations of Hyperfine Coupling Constants for Heavy Heteroatom Radicals.

IF 2.3 3区化学

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

Maciej Witwicki

{"title":"Overcoming Challenges in DFT-Based Calculations of Hyperfine Coupling Constants for Heavy Heteroatom Radicals.","authors":"Maciej Witwicki","doi":"10.1002/cphc.202400978","DOIUrl":"https://doi.org/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 EPR 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 exchange and the Gaussian description of nuclear charge. The relativistic effects were introduced using one-component linear response theory with the second-order Douglas-Kroll-Hess (DKH2) formalism and the fully relativistic four-component Dirac-Kohn-Sham (DKS) method. Our 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":" ","pages":"e202400978"},"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)

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)

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.

IF 2.3 3区化学

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

A Agouri, A Benaddi, N Khossossi, S El Filali, Abderrahman Abbassi, A Hasnaoui, S Taj, B Manaut

{"title":"First-Principles Investigation of 2D o-Al2C2 Monolayer: A High-Performance Anode for Li/Na-ion Batteries.","authors":"A Agouri, A Benaddi, N Khossossi, S El Filali, Abderrahman Abbassi, A Hasnaoui, S Taj, B Manaut","doi":"10.1002/cphc.202500025","DOIUrl":"https://doi.org/10.1002/cphc.202500025","url":null,"abstract":"Development of novel anode materials with superior electrochemical performanceis imperative for advancing next-generation high-performance recharge able batteries beyond current limitations. In this study, we present a 2D o-Al2C2 monolayer as a promising lightweight candidate for lithium and sodium-ion battery systems, based on the density functional theory (DFT) investigations and ab initio molecular dynamics (AIMD) simulations. Our comprehensive investigation demonstrates that the o-Al2C2 monolayer ex-hibits remarkable stability with a cohesive energy of -5.30 eV/atom and maintains its structural integrity at room temperature during extended AIMD simulations. The o-Al2C2 monolayer demonstrates exceptional electrochem ical characteristics for Li and Na storage: theoretical specific capacities of 3780.42 mA.h.g-1 and 3436.75 mA.h.g-1, optimal average open circuit volt ages of 0.81 V 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":" ","pages":"e202500025"},"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

Suppressing Halide Segregation in Wide-Bandgap Perovskite Absorbers by Transamination of Formamidinium.

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-03-27 DOI: 10.1002/cphc.202500022

Georgios Loukeris, Clemens Baretzky, Dmitry Bogachuk, Audrey E Gillen, Bowen Yang, Jiajia Suo, Waldemar Kaiser, Edoardo Mosconi, Filippo De Angelis, Gerrit Boschloo, Andreas W Bett, Uli Würfel, Markus Kohlstädt

{"title":"Suppressing Halide Segregation in Wide-Bandgap Perovskite Absorbers by Transamination of Formamidinium.","authors":"Georgios Loukeris, Clemens Baretzky, Dmitry Bogachuk, Audrey E Gillen, Bowen Yang, Jiajia Suo, Waldemar Kaiser, Edoardo Mosconi, Filippo De Angelis, Gerrit Boschloo, Andreas W Bett, Uli Würfel, Markus Kohlstädt","doi":"10.1002/cphc.202500022","DOIUrl":"https://doi.org/10.1002/cphc.202500022","url":null,"abstract":"All-perovskite tandem solar cells are emerging at a fast rate because of their potential to exceed efficiencies of Si-perovskite tandems, in combination with faster manufacturing, lower cost and the ability to be processed on flexible substrates. Mixing halides is key to achieve wide band gap absorbers, which however suffer from halide segregation under illumination resulting in lowering of the band gap. To tackle this problem, butylamine (BA) has been added to the perovskite precursor solution and was found to react with the formamidinium (FA) cation, producing N-butylformamidinium (BuFA) which accumulates at the perovskite surface and grain boundaries. The creation of the BuFA cation results in suppressed halide segregation and improved crystallization. Density functional theory calculations propose the reduction of halide defect formation upon addition of BA, being key to stabilize mixed-halide perovskites. Lastly, we observe a more stable performance of single junction p-i-n perovskite solar cells with addition of BA under constant illumination at 65°C.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500022"},"PeriodicalIF":2.3,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143718111","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

N-Heterocyclic Carbenes: A Βenchmark Study on their Singlet-Triplet Energy Gap as a Critical Molecular Descriptor.

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-03-27 DOI: 10.1002/cphc.202500012

Konstantinos P Zois, Andreas A Danopoulos, Demeter Tzeli

{"title":"N-Heterocyclic Carbenes: A Βenchmark Study on their Singlet-Triplet Energy Gap as a Critical Molecular Descriptor.","authors":"Konstantinos P Zois, Andreas A Danopoulos, Demeter Tzeli","doi":"10.1002/cphc.202500012","DOIUrl":"https://doi.org/10.1002/cphc.202500012","url":null,"abstract":"N-Heterocyclic Carbenes (NHC) are used extensively in modern chemistry and materials science. The in-depth understanding of their electronic structure and of their metal complexes remains an important topic of research and of experimental and theoretical interest. Herein, in contrast to the commonly used HOMO-LUMO(H-L) gap or Singlet-Triplet(S-T) vertical gap due to the simplicity of their calculations, which occasionally leads to controversial results, we establish the adiabatic singlet-triplet gap as a superior, quantifiable critical descriptor, sensitive to the nature and the structural diversity of the NHCs, for a successful rationalization of experimental observations and computationally extracted trends. The choice was supported by a benchmark study on the electronic structures of NHCs, using high-level ab initio methods, i.e., CASSCF, NEVPT2, MRCISD, DLNPO-CCSD(T) along with DFT methods such as BP86, M06, and M06-L, B3LYP, PBE0, TPSSh, CAM-B3LYP, and B2PLYP. It is found that the adiabatic S-T gap of the NHCs or their complexes is more sensitive to the nature and structural features of the NHCs and not to the type of the used methodology, or the used functional within DFT, and thus fulfils to an extent the requirements for a critical parameter.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500012"},"PeriodicalIF":2.3,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143718109","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

Exploring Quality Criteria for the Computational Modeling of Heterogeneous Catalysts.

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-03-26 DOI: 10.1002/cphc.202401123

Florian Goeltl

引用次数: 0

Computational Evaluation of Redox Potentials of Metal Complexes for Aqueous Flow Batteries.

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-03-26 DOI: 10.1002/cphc.202500046

Aliyeh Mehranfar, Jenna Hannonen, Ali Tuna, Maryam Jafarishiadeh, Anniina Kiesilä, Petri Pihko, Pekka Peljo, Kari Laasonen

{"title":"Computational Evaluation of Redox Potentials of Metal Complexes for Aqueous Flow Batteries.","authors":"Aliyeh Mehranfar, Jenna Hannonen, Ali Tuna, Maryam Jafarishiadeh, Anniina Kiesilä, Petri Pihko, Pekka Peljo, Kari Laasonen","doi":"10.1002/cphc.202500046","DOIUrl":"https://doi.org/10.1002/cphc.202500046","url":null,"abstract":"Flow batteries are a promising option for large-scale stationary energy storage, but better redox active materials are required. Computational Density Functional Theory (DFT) approach to materials screening can identify the most promising avenues and accelerate the development of the technology. In this work, we focus on metal complexes with functionalized organic ligands. The right redox potential, good chemical stability, and high solubility are the main characters in designing a high-performance aqueous electrolyte. Here, Fe, Ti, Mn, and Ni are studied as central metals of the complexes with two ligand classes containing N- and O- groups. The accuracy of the DFT redox potentials is compared to experiments whenever available. In addition, some cyclic voltammetry measurements were performed for Fe-bipyridine, phenanthroline and terpyridine complexes. We have evaluated the computational redox potentials for ca.180 different metal-ligand combinations. Overall, this work presents a new insight into the design of new electrolytes for aqueous flow batteries.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202500046"},"PeriodicalIF":2.3,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143708867","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