Physical Chemistry Chemical Physics最新文献

{"title":"Prediction of solution phase association constants by mapping contact points in intermolecular complexes.","authors":"Katarzyna J Zator,Christopher A Hunter","doi":"10.1039/d5cp00398a","DOIUrl":"https://doi.org/10.1039/d5cp00398a","url":null,"abstract":"Atomic surface site interaction points (AIP) provide a complete description of the non-covalent interactions that one molecule can make with another. The surface site interaction model for the properties of liquids at equilibrium (SSIMPLE) algorithm can be used to calculate the free energy change associated with the pairwise interaction between two AIPs on two different molecules in any solvent. Summing these pairwise AIP interactions across an intermolecular interface that involves multiple interacting sites can be used to calculate solution phase binding free energies and association constants. A computational tool that converts the three-dimensional structure of a complex into a set of AIP contacts has been developed along with a visualisation tool to display AIP interaction maps, allowing straightforward identification of the key intermolecular contacts that contribute most to the overall binding free energy in a complex. The method successfully reproduces solution phase association constants (to within an order of magnitude) for a range of host-guest complexes involving H-bonding, aromatic and hydrophobic interactions, but performs less well for halogen-bonds and complexes involving interactions between the extended π-surfaces of fullerene-type compounds.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"14 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144087735","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}

{"title":"Substrate charge transfer drives the absorption site of metal-phthalocyanines and porphyrins on coinage metal surfaces","authors":"Silvia Carlotto, Iulia Cojocariu, Vitaliy Feyer, Luca Schio, Luca Floreano, Maurizio Casarin","doi":"10.1039/d5cp01576f","DOIUrl":"https://doi.org/10.1039/d5cp01576f","url":null,"abstract":"The frontier electronic structure of tetraphenylporphyrinato (TPP<small>^2-</small>) and phthalocyaninato (Pc<small>^2-</small>) square planar transition metal complexes (MTPP and MPc; M = V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) has been revisited through DFT calculations. The different symmetry and spin multiplicity between MPc and MTPP of the same M is shown to originate from the different Pc<small>^2-</small> and TPP<small>^2-</small> ligand field, stronger in the former ligand than in the latter. The corresponding spatial localization and symmetry of the unoccupied molecular orbitals postulate unescapable geometric constraints to their overlap with the electron cloud of a crystalline metal surface. From comparison with literature experimental evidence, we show that the adsorption geometry (atomic site and azimuthal orientation) of MTPPs and MPcs on the low index crystal planes of coinage metals (CM = Au, Ag, Cu) may be predicted when two conditions are satisfied: i) evidence of a surface → adsorbate charge transfer, ii) absence of significant distortion of the macrocycle upon adsorption. In this regard, the overall susceptibility to charge transfer is determined by the strength of the molecular ligand field (i.e., charge transfer to MPc is more favoured than to MTPP) and inversely linked to the electronegativity of the surface atoms (being Au the most inert CM substrate thanks to its highest electronegativity).","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"77 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066170","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}

{"title":"Persistence of Ce3+ Species on the Surface of Ceria during Redox Cycling: A Modulated Chemical Excitation Investigation","authors":"Cyril Hachemi, Hadi Dib, Mourad Debbichi, Michael Badawi, Calley Eads, Maya Ibrahim, Stéphane Loridant, Jan Knudsen, Helena Kaper, Luis Cardenas","doi":"10.1039/d5cp01283j","DOIUrl":"https://doi.org/10.1039/d5cp01283j","url":null,"abstract":"Operando Resonant Photoelectron Spectroscopy (RPES) combined with Modulated Chemical Excitation revealed the dynamic evolution of Ce<small>³⁺</small> and Ce<small>⁴⁺</small> redox states at the surface of CeO<small>₂</small> during the CO oxidation reaction. Using alternating CO and O<small>₂</small> pulses as chemically modulated signals, we monitored the surface states in the valence band region, unveiling the evolution of electronic structure during the catalytic process. The analysis with different gas flow ratios revealed that under CO-rich conditions (CO:O<small>₂</small> ≥ 1), only partial conversion from Ce<small>³⁺</small> to Ce<small>⁴⁺</small> occurred. In contrast, complete Ce<small>³⁺</small> to Ce<small>⁴⁺</small> conversion was achieved when pulsing O<small>₂</small> into O<small>₂</small>-rich environments. Furthermore, we find that intermediate oxygen species, such as peroxo and OH, impact the conversion of Ce<small>³⁺</small> and Ce<small>⁴⁺</small>. These oxygenated species coexist between 330 °C and 360 °C in pure O<small>₂</small>, while above 390 °C only OH groups remain stable on the ceria surface.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"78 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066135","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}

{"title":"Excitations in Lanthanide Ions: A Systematic Evaluation of two-component CAS-CI and GW","authors":"Roman Zielke, Florian Weigend, Christof Holzer","doi":"10.1039/d5cp00780a","DOIUrl":"https://doi.org/10.1039/d5cp00780a","url":null,"abstract":"This paper presents a thorough prediction and investigation of ionization energies, atomic levels, and crystal-field splittings in lanthanide ions. We show that a two-component complete active space (CAS) configuration interaction (CI) approach based on two-component density functional theory (DFT) reference states is suitable to yield accurate excitation energies for lower energy terms. DFT references are further shown to be superior to Hartree-Fock (HF) references for predicting both atomic levels and ionization energies. Especially in the Greens function based GW method used to determine ionization energies, the deficiencies of the wave function based HF references are severe, leading to sizable errors. Two-electron contributions to spin-orbit coupling are found to be an important ingredient for obtaining accurate atomic levels. These contributions are taken into account using a screened-nuclear-spin-orbit (SNSO) approach, which is shown to be very accurate. DFT based CAS-CI is further used to calculate crystal-field splittings. The results are well suited to predict the subtle splittings in complexes with unpaired 4f electrons.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"6 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066136","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}

{"title":"Machine-Learning molecular dynamics simulations of Shock Response and Spallation Behavior in PPTA Crystals","authors":"lei liu, Jingfu Shi, Di Song, Changqing Miao","doi":"10.1039/d5cp00251f","DOIUrl":"https://doi.org/10.1039/d5cp00251f","url":null,"abstract":"The shock response of poly(p-phenylene terephthalamide) (PPTA) crystals is investigated using molecular dynamics simulations combined with a machine learning potential. Considering the anisotropy of PPTA crystals, the directions dominated by hydrogen bonding and van der Waals forces are examined, respectively. First, a machine learning potential capable of simulating the shock behavior of PPTA is developed and validated. The potential is demonstrated to achieve excellent accuracy, showing high consistency with density functional theory results. Based on the established machine learning potential, multiscale shock techniques are employed to simulate shock compression at various particle velocities. The Hugoniot curves of PPTA crystals reveal three distinct stages of shock response: elastic, plastic, and cross-linking. With increasing particle velocity, the b axis of PPTA crystals is found to exhibit a greater tendency for plastic deformation. Plasticity along the a axis is characterized by the planarization of adjacent benzene rings within the chains, while along the b axis, it involves the breaking and reformation of hydrogen bonds. The spatiotemporal evolution of thermodynamic parameters and spallation during shock wave propagation is further uncovered through non-equilibrium molecular dynamics simulations. The shock response mechanisms of PPTA fibers are elucidated, providing a foundation for subsequent simulations and their application in impact protection structures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"30 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066139","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}

{"title":"Predicting accurate binding energies and vibrational spectroscopic features of interstellar icy species. A quantum mechanical study","authors":"Albert Rimola, Alicja Bulik, Berta Martínez-Bachs, Niccolò Bancone, Eric Mates-Torres, Marta Corno, Piero Ugliengo","doi":"10.1039/d5cp01151e","DOIUrl":"https://doi.org/10.1039/d5cp01151e","url":null,"abstract":"In the coldest, densest regions of the interstellar medium (ISM), dust grains are covered by thick ice mantles dominated mainly by water. Although more than 300 species have been detected in the gas phase of the ISM by their rotational emission lines within the radio frequency range, only a few were found in interstellar ices, e.g. CO, CO<small>₂</small>, NH<small>₃</small>, CH<small>₃</small>OH, CH<small>₄</small> and OCS, by means of infrared (IR) spectroscopy. Observations of ices require a background-illuminating source for absorption, constraining the available sight lines for investigation. Further challenges arise when comparing with laboratory spectra due to the influence of temperature, ice structure and the presence of other species. In the era of IR observations provided by the James Webb Space Telescope (JWST), it is crucial to provide reference spectral data confirming JWST's assigned features. For this purpose, this study addresses the adsorption of the aforementioned species on water ice surfaces and their IR features by means of quantum chemical computations grounded on the density functional theory (DFT) hybrid B3LYP-D3(BJ) functional, known to give reliable results for binding energy and vibrational frequency calculations, including IR spectra simulation. The calculated binding energies and IR spectral data are presented in the context of experimental spectra of ices and the new findings from the JWST, which have already proven to be insightful thanks to its unmatched sensitivity. We show that quantum chemistry is a powerful tool for accurate frequency calculations of ISM ice interfaces, providing unprecedented insights into their IR signatures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066137","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}

{"title":"Tuning surface curvature in B and N co-doped CNT-derived Fe, Ru and Ir catalysts for electrochemical hydrogenation of N2 to NH3.","authors":"Deewan S Teja,Bhabani S Mallik","doi":"10.1039/d5cp00309a","DOIUrl":"https://doi.org/10.1039/d5cp00309a","url":null,"abstract":"Single-atom catalysts (SACs) have tremendous applications in enhancing the catalytic performance in the electrocatalytic nitrogen reduction reaction (NRR). Carbon-based substrates have superior properties that improve the catalytic performance either by forming defects or by doping heteroatoms, such as B,N-doped graphene, S-doped graphene, and defective carbon nanotubes. However, the carbon nanotube (CNT)-based electrocatalysts for NRR study are currently less explored. Here, we use the FeB2N2-(n,0) CNTs (n = 3-8) as representative electrocatalysts to study the different CNT curvatures and reveal their effects on the NN triple bond activation and adsorption free energy (ΔG) of the *N2 molecule, with changes in the potential-determining step in NRR. Zigzag B2N2-(6,0) CNTs were selected as the efficient substrate, with three transition metal atoms (TM = Fe, Ru and Ir) anchored on the B2N2-(6,0) CNT to construct the NRR catalysts. Using first-principles calculation and the computational hydrogen electrode (CHE) model, we investigated their electrocatalytic performance in NRR. FeB2N2-(6,0) CNT is the most efficient catalyst and has a low limiting potential (UL) of -0.551 V for NRR. Further, the projected partial density of states and projected crystal orbital Hamilton population analyses illustrate that the N2 activation is due to strong π*-backbonding, which leads to effective charge transfer between the active site (metal d-orbital) and N2 molecule (p-orbital). The FeB2N2-(6,0) CNT also showed high NRR selectivity, inhibiting the competitive hydrogen evolution reaction. Our study provides a detailed mechanism of catalysis by the carbon-based, high-efficiency electrocatalyst for NRR and opens up the possibility for experimentalists to further explore the carbon-based one-dimensional electrocatalyst for NRR.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"36 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144065656","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}

{"title":"Fabrication of gold/polyaniline/copper oxide electrode for efficient photoelectrochemical hydrogen evolution.","authors":"Fahad Abdulaziz,Mohamed Zayed,Salman Latif,Yassin A Jeilani,Mohamed Shaban,Raja Rama Devi Patel,Hussein A Elsayed,Mohamed Rabia,Ashour M Ahmed","doi":"10.1039/d5cp00350d","DOIUrl":"https://doi.org/10.1039/d5cp00350d","url":null,"abstract":"This study explores a novel photoelectrode composed of copper oxide (CuO), polyaniline (PANI), and gold (Au) for efficient hydrogen production through photoelectrochemical (PEC) water splitting. Structural and morphological analyses using various techniques confirm the successful fabrication of the ternary Au/PANI/CuO photoelectrode. The integration of Au, PANI, and CuO nanomaterials enhances light harvesting, facilitates charge transfer, and reduces charge recombination due to the plasmonic effect of Au and the synergistic interaction between PANI and CuO. The Au/PANI/CuO photoelectrode achieves a 300-fold increase in photocurrent density (15 mA cm-2 at -0.39 V vs. RHE) compared to pure CuO. Additionally, it demonstrates superior operational stability for 5 hours and records an IPCE of 45% at 500 nm. These findings pave the way for the development of high-performance and durable plasmonic/polymer/semiconductor photoelectrodes for sustainable and clean hydrogen generation.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"53 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144065957","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}

{"title":"Quantitative modeling of point defects in β-Ga2O3 combining hybrid functional energetics with semiconductor and processes thermodynamics","authors":"K. A. Arnab, M. Stephens, I. Maxfield, C. Lee, E. Ertekin, Y. K. Frodason, J. B. Varley, M. A. Scarpulla","doi":"10.1039/d4cp04817b","DOIUrl":"https://doi.org/10.1039/d4cp04817b","url":null,"abstract":"β-Gallium oxide (β-Ga<small>₂</small>O<small>₃</small>) is of high interest for power electronics because of its unique combination of melt growth, epitaxial growth, n-type dopability, ultrawide bandgap, and high critical field. Optimization of crystal growth processes to promote beneficial defects and suppress harmful ones requires accurate quantitative modelling of both native and impurity defects. Herein we quantitatively model defect concentrations as a function of bulk crystal growth conditions and demonstrate the necessity of including effects such as bandgap temperature dependence, chemical potentials from thermochemistry, and defect vibrational entropy in modelling based on defect formation energies computed by density functional theory (DFT) with hybrid functionals. Without these contributions, grossly-erroneous and misleading predictions arise, <em>e.g.</em> that n-type doping attempts would be fully compensated by Ga vacancies. Including these effects reproduces the experimental facts that melt-grown Sn-doped β-Ga<small>₂</small>O<small>₃</small> crystals are conductive with small compensation while annealing the same crystals in O<small>₂</small> at intermediate temperatures renders them insulating. To accomplish this modeling, we developed a comprehensive modelling framework (KROGER) based on calculated defect formation energies and flexible thermodynamic conditions. These capabilities allow KROGER to capture full and partial defect equilibria amongst native defects and impurities occurring during specific semiconductor growth or fabrication processes. We use KROGER to model 873 charge-states of 259 defects involving 19 elements in conditions representing bulk crystal growth by edge-fed growth (EFG) and annealing in oxygen. Our methodology is transferrable to a wide range of materials beyond β-Ga<small>₂</small>O<small>₃</small>. The integration of thermodynamic and first-principles modelling of point defects provides insight into optimization of point defect populations in growth and processing.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"42 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066172","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}

{"title":"Nanoscale island manipulation and construction of heterojunctions by mechanical collision of 2D materials.","authors":"Xiongbai Cao,Liangguang Jia,Huixia Yang,Zhenru Zhou,Tingting Wang,Haolong Fan,Yan Li,Xiaoyu Hao,Lingtao Zhan,Qinze Yu,Liwei Liu,Teng Zhang,Quanzhen Zhang,Yeliang Wang","doi":"10.1039/d5cp01339a","DOIUrl":"https://doi.org/10.1039/d5cp01339a","url":null,"abstract":"Controllable phase transitions between distinct polymorphs in transition metal dichalcogenides (TMDs) hold great significance for applications in nanoscale electronics. Currently, constructing nanoscale heterojunctions with the desired TMD phase remains challenging due to insufficient control. In this study, we provided a new strategy of phase transitions by controllable mechanical collision of TMD islands containing over thousands of atoms. Using an in situ scanning tunneling microscopy (STM) tip manipulation technique, we can precisely control the fixed-axis rotation of nanoscale NbSe2 islands. Through mechanically colliding T- and H-NbSe2 with each other, we successfully triggered a phase transition from Mott insulator T-NbSe2 to semi-metal H-NbSe2, thereby creating a high-quality heterojunction. We further unveiled the unusual electronic properties of this heterojunction, and provided new insights into the phase transition mechanisms in TMDs and their potential applications in nanoscale electronics.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"28 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144065657","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}