Physical Chemistry Chemical Physics最新文献_第6页

Analysis of Bijel Formation Dynamics During Solvent Transfer-Induced Phase Separation Using Phase-Field Simulations

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-14 DOI: 10.1039/d4cp04638b

Jesse M. Steenhoff, Martin Haase

{"title":"Analysis of Bijel Formation Dynamics During Solvent Transfer-Induced Phase Separation Using Phase-Field Simulations","authors":"Jesse M. Steenhoff, Martin Haase","doi":"10.1039/d4cp04638b","DOIUrl":"https://doi.org/10.1039/d4cp04638b","url":null,"abstract":"Solvent transfer induced phase separation (STrIPS) is a versatile and scalable method for the fabrication of bicontinuous interfacially jammed emulsion gels (bijels), a soft material with ample potential in membrane separation and energy storage. STrIPS, however, does not facilitate in-situ observation of bijel formation, rendering it difficult to relate the phase separation process to the resulting bijel morphology. To address this issue, a phase-field (PF) model is presented that captures the principle components of STrIPS through relatively simple methods. Comparison with experimental results demonstrates that the PF model accurately describes STrIPS, reproducing morphological trends in a complex experimental system. Simultaneously, the model provides insight into the origin of such morphological features, relating the formation of the bijel structure in STrIPS to relatively slow dynamics of phase separation compared to solvent diffusion. Visualizing phase separation during the entire STrIPS process, the PF model can therefore help elucidate the formation mechanisms underlying current STrIPS bijel morphologies, in addition to aiding the fabrication of novel ones.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"31 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418143","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

Predicting and interpreting EPR spectra of POPC lipid bilayers with transmembrane α-helical peptides from all-atom molecular dynamics simulations.

IF 2.9 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-14 DOI: 10.1039/d4cp04802d

Andrea Catte, Vasily S Oganesyan

{"title":"Predicting and interpreting EPR spectra of POPC lipid bilayers with transmembrane α-helical peptides from all-atom molecular dynamics simulations.","authors":"Andrea Catte, Vasily S Oganesyan","doi":"10.1039/d4cp04802d","DOIUrl":"https://doi.org/10.1039/d4cp04802d","url":null,"abstract":"This study reports a large-scale all-atom MD simulation of POPC lipid bilayers in the presence of different concentrations of the transmembrane peptide acetyl-K2(LA)12K2-amide ((LA)12) and doped with 5-PC paramagnetic spin probes used in EPR studies. We apply a combined MD-EPR simulation methodology for the prediction of EPR spectra directly and completely from MD trajectories. This approach serves three major purposes. Firstly, comparing predicted EPR spectra with experimental ones, which are highly sensitive to motions, provides an ultimate test bed for the force fields currently employed for modeling lipid bilayer systems with embedded proteins or peptides. Secondly, simulations of EPR spectra directly from the atomistic MD models simplify the interpretation of the EPR line shapes and their changes induced by the presence of peptides in the lipid bilayer. These changes are directly linked to the dynamics and order of spin probes and POPC host molecules. Lastly and importantly, we demonstrate how the MD-EPR methodology can be employed to test the validity and limitations of the widely used approach for the estimation of the order parameter of lipids directly from the EPR experimental line shapes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143412442","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

Energy transfer booster: How a leaving group controls the excited state pathway within a caging BASHY-BODIPY dyad

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-14 DOI: 10.1039/d4cp04776a

Yagmur Aydogan-Sun, Maximiliane Horz, Rebekka Weber, Myron Heinz, Markus Braun, Alexander Heckel, Irene Burghardt, Josef Wachtveitl

{"title":"Energy transfer booster: How a leaving group controls the excited state pathway within a caging BASHY-BODIPY dyad","authors":"Yagmur Aydogan-Sun, Maximiliane Horz, Rebekka Weber, Myron Heinz, Markus Braun, Alexander Heckel, Irene Burghardt, Josef Wachtveitl","doi":"10.1039/d4cp04776a","DOIUrl":"https://doi.org/10.1039/d4cp04776a","url":null,"abstract":"Photocages are powerful tools for spatiotemporal control of molecule release or biological activity. However, many photocages are unsuitable for biological experiments since they are mostly activated by harmful ultraviolet (UV) light and often lack a sufficient optical readout. Thus, there is a high demand for near infrared (NIR) and/or two-photon activatable photocages with a characteristic readout. In this report, we will study an intramolecular energy-transfer system based on a BASHY fluorophore serving as a two-photon antenna for a poorly two-photon absorbing BODIPY photocage. The herein investigated systems, with and without leaving group (LG), show different excitation energy transfer (EET) efficiencies and therefore differ in their fluorescence properties. To understand the molecular basis for these significant differences, detailed spectroscopic and theoretical analyses were employed from ultrafast transient absorption spectroscopy to excited-state calculations and quantum dynamical modelling. The result of our comprehensive study reveals the pivotal role of the LG as an EET booster through specific pathway guidance. In contrast, without the LG, the EET efficiency is reduced and the excitation energy predominantly dissipates within the BASHY chromophore. The present study highlights that LGs can actively contribute to optimizing the properties of dyad based systems and offers new design principles for monitoring uncaging via an intrinsic fluorescence readout.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"3 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418140","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

Integrating Density Functional Theory with Machine Learning for Enhanced Band Gap Prediction in Metal Oxides

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-14 DOI: 10.1039/d4cp03397c

Chidozie Ezeakunne, Bipin Lamichhane, Shyam Kattel

{"title":"Integrating Density Functional Theory with Machine Learning for Enhanced Band Gap Prediction in Metal Oxides","authors":"Chidozie Ezeakunne, Bipin Lamichhane, Shyam Kattel","doi":"10.1039/d4cp03397c","DOIUrl":"https://doi.org/10.1039/d4cp03397c","url":null,"abstract":"In this study, we used a combination of density functional theory with Hubbard U correction (DFT+U) and machine learning (ML) to accurately predict the band gaps and lattice parameters of metal oxides: TiO2 (rutile and anatase), cubic ZnO, cubic ZnO2, cubic CeO2, and cubic ZrO2. Our results show that including Up values for oxygen 2p orbitals alongside Ud/f for metal 3d or 4f orbitals significantly improves the band gap and lattice parameters predictions. Through extensive DFT+U calculations, we identified optimal (Up, Ud/f) integer pairs that closely matched the experimental values for band gaps and lattice parameters: (8 eV, 8 eV) for rutile TiO2, (3 eV, 6 eV) for anatase TiO2, (6 eV, 12 eV) for c-ZnO, (10 eV, 10 eV) for c-ZnO2, (9 eV, 5 eV) for c-ZrO2 and (7 eV, 12 eV) for c-CeO2. Our ML analysis demonstrated that simple supervised ML models can reliably achieve accuracy comparable to DFT+U calculations. These models have the potential to extend beyond the metal oxides used in training and to explore the effects and dependencies of U values on the bulk properties of materials. Our study not only identifies the best U pairs for predicting experimentally measured band gaps and lattice parameters but also highlights the effectiveness of straightforward regression ML models in predicting the band gaps and lattice parameters of metal oxides.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"64 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418141","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

Accurate incorporation of hyperfine coupling in diabatic potential models using the Effective Relativistic Coupling by Asymptotic Representation approach

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-14 DOI: 10.1039/d4cp04170d

Maik Vossel, Iordanis Tsakontsis, Nicole Weike, Wolfgang Eisfeld

{"title":"Accurate incorporation of hyperfine coupling in diabatic potential models using the Effective Relativistic Coupling by Asymptotic Representation approach","authors":"Maik Vossel, Iordanis Tsakontsis, Nicole Weike, Wolfgang Eisfeld","doi":"10.1039/d4cp04170d","DOIUrl":"https://doi.org/10.1039/d4cp04170d","url":null,"abstract":"The accurate treatment of relativistic couplings like spin-orbit (SO) coupling into diabatic potential models is highly desirable. We have been developing the Effective Relativistic Coupling by Asymptotic Representation (ERCAR) approach to this end. The central idea of ERCAR is the representation of the system using an asymptotic diabatic direct product basis of atom and fragment states. This allows to treat relativistic coupling operators like SO coupling analytically. This idea is extended here to the incorporation of hyperfine (HF) coupling into the diabatic potential model. Hyperfine coupling is due to the magnetic dipole-dipole and the Fermi contact interaction as well as the electric quadrupole interaction. The corresponding operators can be expressed in terms of the angular momentum operators for nuclear spin $hat I$ and for total angular momentum $hat J$ of the atomic fine structure states. The diabatic basis of an existing ERCAR model is complemented by nuclear spinors and the HF coupling operators are easily evaluated in that basis. Diagonalization of the resulting full diabatic ERCAR model yields the HF energies and states for any molecular geometry of interest. The new method is demonstrated using an existing accurate diabatic potential model for hydrogen iodide (HI)[J. Chem. Phys. 159 244119 (2023)] to see the effects of hyperfine coupling. The HF coupling effect of the 2P3/2 ground state and spin-orbit excited 2P1/2 state of iodine combined with the 2S1/2 ground state of hydrogen are added to the ERCAR Hamiltonian. It is shown that each fine structure state is split by the hyperfine interactions into sets of seven hyperfine states. The fine structure ground state at the global minimum is split into three degenerate groups of hyperfine states with splittings of 152 and 76 MHz.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"51 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418094","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 molecular wires for efficient photo-generation of free electric charge carriers

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-13 DOI: 10.1039/d5cp00025d

Mikołaj Martyka, Joanna Jankowska

引用次数: 0

Anti-Kasha’s rule for semiconductor photocatalytic reactions: The wavelength dependence of quantum efficiency

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-13 DOI: 10.1039/d4cp03976a

Yuhan Lin, Yi He, Qiang Wang, Jie Feng, Yue Hou, Chuanyi Wang

引用次数: 0

Ga Adlayer Model: Capturing Features of GaN(0001) Growth from Submonolayer to Multilayer Regime

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-13 DOI: 10.1039/d4cp04688a

Razia ., Madhav Ranganathan

{"title":"Ga Adlayer Model: Capturing Features of GaN(0001) Growth from Submonolayer to Multilayer Regime","authors":"Razia ., Madhav Ranganathan","doi":"10.1039/d4cp04688a","DOIUrl":"https://doi.org/10.1039/d4cp04688a","url":null,"abstract":"The morphology of GaN(0001) thin films grown by molecular beam epitaxy is dependent on the ratio of the gallium to nitrogen flux. Films grown under gallium-rich conditions form smooth surfaces while those grown under nitrogen-rich conditions result in rough, pitted surfaces. This difference is attributed to the high barrier for surface diffusion of nitrogen, which is remedied by the surfactant effect of gallium under excess gallium conditions. We construct a two-component solid-on-solid model and implement lattice-based kinetic Monte Carlo (kMC) simulations to study homoepitaxial growth of GaN(0001). We explicitly account for gallium adlayer formation and diffusion of nitrogen below the surface Ga layer. The initial stages of growth in these simulations show the evolution of submonolayer islands from random clusters to ordered triangular islands. On subsequent growth, we find that films grown in excess gallium conditions are significantly smoother compared to those grown in nitrogen rich or stoichiometric conditions. From the surface roughness for different atomic flux and temperature, we obtain the optimal conditions for growth of smooth films. We extend the study to vicinal surface growth and show how the surface shows a tendency towards step-flow growth in Ga-rich conditions. Our results are consistent with experiments that illustrate a change in growth mode for homoepitaxy on vicinal GaN(0001) surfaces.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"1 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401912","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

Rational design of surface termination of Ti3C2T2 MXenes for lithium-ion battery anodes

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-13 DOI: 10.1039/d4cp04583a

Meng Tian

{"title":"Rational design of surface termination of Ti3C2T2 MXenes for lithium-ion battery anodes","authors":"Meng Tian","doi":"10.1039/d4cp04583a","DOIUrl":"https://doi.org/10.1039/d4cp04583a","url":null,"abstract":"Two-dimensional transition metal carbides, carbonitrides and nitrides (MXenes) have garnered increasing interest in the energy storage field due to their unique structural and electronic properties. However, the application performance is highly reliant on the surface termination, which is poorly understood from a chemical standpoint. In this work, the structural stability, chemical origin, electronic structure and lithium-ion (Li-ion) storage properties of 15 nonmetal terminated MXenes in the form of Ti3C2T2 (T = B, C, Si, N, P, As, O, S, Se, Te, F, Cl, Br, I and OH) were investigated using first-principles calculations. The results indicate that the partially occupied d-orbital and zero pseudogap lead to the high chemical activity of surface Ti, and that surface terminations can diminish its chemical activity. Furthermore, a large pseudogap of the d-orbital promotes the structural stability of Ti3C2T2. A useful descriptor, the antibonding state (Eσ*), was proposed to predict Li-ion adsorption energy. Combining the good electronic conductivity, high lithophilicity, low Li-ion diffusion barrier and high specific capacity, Ti3C2As2, Ti3C2S2 and Ti3C2Se2 are considered as promising anode candidates for Li-ion batteries. Additionally, S, Se and As doping can improve the Li-ion storage performance of oxygen terminated Ti3C2O2. This work offers insights into the chemical origin of the surface termination and paves the way for designing excellent Li-ion anode candidates based on MXenes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"32 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143401848","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-Principle Oligopeptide Structural Optimization with Physical Prior Mean-Driven Gaussian Processes: A Test of Synergistic Impacts of the Kernel Functional and Coordinate System 利用物理先验均值驱动的高斯过程进行第一原理寡肽结构优化：检验核函数和坐标系的协同影响

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-02-12 DOI: 10.1039/d4cp04378b

Yibo Chang, Chong Teng, Junwei Lucas Bao

{"title":"First-Principle Oligopeptide Structural Optimization with Physical Prior Mean-Driven Gaussian Processes: A Test of Synergistic Impacts of the Kernel Functional and Coordinate System","authors":"Yibo Chang, Chong Teng, Junwei Lucas Bao","doi":"10.1039/d4cp04378b","DOIUrl":"https://doi.org/10.1039/d4cp04378b","url":null,"abstract":"First-principle molecular structural determination is critical in many aspects of computational modeling, and yet, the precise determination of a local minimum for a large-sized organic molecule is time-consuming. The recently developed nonparametric model, the physical Gaussian Processes (GPs) with physics-informed prior mean function, has demonstrated its efficiency in exploring the potential-energy surfaces and molecular geometry optimizations. Two essential ingredients in physical GPs, the kernel functional and the coordinate systems, could impact the optimization efficiency, and yet the choice of which on the model performance has not yet been studied. In this work, we constructed a testing dataset consisting of 20 oligopeptides and performed a systematic investigation using various combinations of coordinates (structural descriptors) and kernel functionals to optimize these biologically interesting molecules to local minima at the density-functional tight-binding (DFTB) quantum mechanical level. We conclude that the combination of the kernel functional form and coordinate systems matter significantly in model performance as well as its robustness in locating local minima. For our testing set, the synergy between the periodic kernel and the non-redundant delocalized internal coordinates yields the best overall performance for physical GPs, significantly superior to other choices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"78 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393725","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