Physical Chemistry Chemical Physics最新文献_第2页

Combining the Maximum Overlap Method with Multiwavelets for Core-Ionisation Energy Calculations 结合最大重叠法与多小波计算核电离能

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp01544h

Niklas Göllmann, Matthew R. Ludwig, Peter Wind, Laura E. Ratcliff, Luca Frediani

{"title":"Combining the Maximum Overlap Method with Multiwavelets for Core-Ionisation Energy Calculations","authors":"Niklas Göllmann, Matthew R. Ludwig, Peter Wind, Laura E. Ratcliff, Luca Frediani","doi":"10.1039/d5cp01544h","DOIUrl":"https://doi.org/10.1039/d5cp01544h","url":null,"abstract":"We present a protocol for computing core-ionisation energies for molecules, which is essential for reproducing X-Ray photoelectron spectroscopy experiments. The electronic structures of both the ground state and the core-ionised states are computed using Multiwavelets and Density-Functional Theory, where the core ionisation energies are computed by virtue of the ΔSCF method. To avoid the collapse of the core-hole state or its delocalisation, we make use of the Maximum Overlap Method, which provides a constraint on the orbital occupation, while avoiding the use of pseudopotentials. Combining Multiwavelets with the Maximum Overlap Method allows for the first time an all-electron calculation of core-ionisation energies with Multiwavelets, avoiding known issues connected to the use of Atomic Orbitals (slow convergence with respect to the basis set limit, numerical instabilities of core-hole states for large systems). We show that our results are consistent with previous Multiwavelet calculations which made use of pseudopotentials, and are generally more precise than corresponding Atomic Orbital calculations. We analyse the results in terms of precision compared to both Atomic Orbital calculations and Multiwavelets+pseudopotentials calculations. Moreover, we demonstrate how the protocol can be applied to target molecules of relatively large size. Both closed-shell and open-shell methods have been implemented.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"3 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203655","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

Origin of the nonresonant signal in sum-frequency vibrational spectroscopy at the water interface 水界面和频振动谱中非共振信号的来源

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp03270a

Ren-Hui Zheng, Wen-Mei Wei

引用次数: 0

Modulation of Triarylhydrazone Photoswitching Efficiency Through Heteroaryl Variations 杂芳基变化对三芳基腙光开关效率的调节

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp02063h

Lea Hegedüsová, Šimon Budzák, Miroslav Medved, Lukáš F. Pašteka, Juraj Filo, Bernard Mravec, Anna Grabarz, Marek Cigáň

{"title":"Modulation of Triarylhydrazone Photoswitching Efficiency Through Heteroaryl Variations","authors":"Lea Hegedüsová, Šimon Budzák, Miroslav Medved, Lukáš F. Pašteka, Juraj Filo, Bernard Mravec, Anna Grabarz, Marek Cigáň","doi":"10.1039/d5cp02063h","DOIUrl":"https://doi.org/10.1039/d5cp02063h","url":null,"abstract":"Triarylhydrazones (TAHZs) complement the mosaic of recently discovered P-type diarylhydrazone photoswitches. They typically exhibit higher molar absorptivities and operate under light of longer wavelengths, while preserving the attractive features of diarylhydrazones such as excellent addressability and extraordinary thermal stability of both isomers. However, TAHZs often suffer from low quantum yields of the Z-to-E photoisomerization due to a relatively strong excited-state intramolecular hydrogen bonding (IHB) in the Z isomer. Although the presence of IHB ensures the large separation of absorption maxima, it simultaneously leads to competing processes that reduce the efficiency of E-to-Z photoisomerization. Here, we present a strategy of reducing the IHB strength through a suitably chosen variation of heteroaryl, which not only significantly increases the efficiency of the Z-to-E photoreaction but also allows for the maintenance of sufficient addressability due to the reduced intensity of the S0-S1 transition accompanied with the emergence of bright higher excited states of the E isomer.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"3 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203112","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

A Comparative Study on Hydroxyl and Ether Functionalized Ionic Liquid Additives for Defect Passivation and Stability in Perovskite Solar Cells 羟基和醚功能化离子液体添加剂对钙钛矿太阳能电池缺陷钝化和稳定性的比较研究

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp01454a

Sirin Siyahjani Gultekin, Sevdiye Basak Turgut, Saliha Ozdemir, Burak Gültekin, Canan Varlikli

{"title":"A Comparative Study on Hydroxyl and Ether Functionalized Ionic Liquid Additives for Defect Passivation and Stability in Perovskite Solar Cells","authors":"Sirin Siyahjani Gultekin, Sevdiye Basak Turgut, Saliha Ozdemir, Burak Gültekin, Canan Varlikli","doi":"10.1039/d5cp01454a","DOIUrl":"https://doi.org/10.1039/d5cp01454a","url":null,"abstract":"This study systematically investigates the effects of two ionic liquid (IL) additives, 2-(2-methoxyethoxy)-N,N-bis(2-(2-methoxyethoxy)ethyl)-N-methylethanaminium iodide (EtAI) and 2-hydroxy-N,N-bis(2-hydroxyethyl)-N-methylethanaminium iodide (HOAI), on the structural, morphological, optical, and photovoltaic properties of triple-cation perovskite thin films. FT-IR, XRD, XPS, SEM, and AFM analyses were employed to characterize additive-induced modifications, while UV-Vis, PL, and TRPL measurements were utilized to evaluate their optical properties. SEM and AFM results reveal that the hydroxyl (-OH) groups in HOAI and etheric groups in EtAI significantly improve film morphology by enhancing grain size, reducing surface roughness, and refining grain boundaries, thereby promoting more efficient charge transport. Photovoltaic characterization revealed that the film with 3 mmol HOAI exhibited a maximum reverse-scan power conversion efficiency (PCE) of 17.65%, maintaining approximately 85% of its initial efficiency after 1000 hours under ambient conditions. In contrast, the film with 1 mmol EtAI achieved a reverse-scan PCE of 17.17%, although higher EtAI concentrations adversely affected stability. These findings provide valuable insights into the interplay between additive chemistry and perovskite film quality, offering a promising route for improving the efficiency and long-term performance of perovskite solar cells.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"67 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203138","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

Photoluminescence and mechanism insights of isomers D- (-)-Arabinose and L-(+)-Arabinose crystals D-(-)-阿拉伯糖和L-(+)-阿拉伯糖晶体异构体的光致发光及其机理

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp03220b

Qingfeng Wu, chuchu Li, Xintong Li, Yuting Xiao, Qin Ding, Qing Zhou

{"title":"Photoluminescence and mechanism insights of isomers D- (-)-Arabinose and L-(+)-Arabinose crystals","authors":"Qingfeng Wu, chuchu Li, Xintong Li, Yuting Xiao, Qin Ding, Qing Zhou","doi":"10.1039/d5cp03220b","DOIUrl":"https://doi.org/10.1039/d5cp03220b","url":null,"abstract":"Nonconventional luminophores have attracted extensive attention due to their unique photoluminescence (PL) properties, including excitation-dependent emission and persistent room temperature phosphorescence (p-RTP), intermolecular interactions play a key role in clustering-triggered emission (CTE). However, the diversity and complexity of atypical chromophores make it a significant challenge to accurately dissect the intrinsic structure of emissive clusters. In this work, D-(-)-arabinose (D-Arb) and L-(+)-arabinose (L-Arb) stereoisomeric pairs were selected as model systems to conduct comparative analysis of PL properties under controlled crystallization conditions. Experimental results show that D-Arb crystals exhibit a red-shifted emission, with relatively high photoluminescence quantum yield (PLQY) reaching 9.26%, while L-Arb crystals have a longer phosphorescence lifetime of 199.5ms. The study reveals that such differences in PL arise from the differentiated packing of D/L-Arb, which share a homologous molecular skeleton but exhibit distinct spatial configurations. Experimental and theoretical results revealed that D/L-Arb crystals form an abundant network of noncovalent interactions, including hydrogen bonds and short contacts between oxygen atoms. Analysis of key energy components intrinsic to the aggregates—such as electrostatic, polarization, dispersion, and exchange repulsion—indicates that these factors lead to varying degrees of electron delocalization in the emissive clusters. Combined with ab initio dynamics(AIMD), the intrinsic relationship between intermolecular interactions among D/L-Arb molecules and PL properties is more clearly revealed. These findings clarify the stereochemical control of emissive clusters through through-space interactions (TSI) and establish a refined structure-property relationship for the design of optical isomers in CTE engineering.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"75 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203140","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

DFT mechanistic investigation of Wacker-type oxidation of olefins catalyzed by Pd(II) quinoline-2-oxazoline complex: effect of electronic asymmetry of the ligand Pd（II）喹啉-2-恶唑啉配合物催化瓦克尔型烯烃氧化的DFT机理研究：配体电子不对称的影响

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp03677a

Noor U Din Reshi, Tabasum Jan, Tasleema Jan, Muzzaffar Ahmad Bhat

{"title":"DFT mechanistic investigation of Wacker-type oxidation of olefins catalyzed by Pd(II) quinoline-2-oxazoline complex: effect of electronic asymmetry of the ligand","authors":"Noor U Din Reshi, Tabasum Jan, Tasleema Jan, Muzzaffar Ahmad Bhat","doi":"10.1039/d5cp03677a","DOIUrl":"https://doi.org/10.1039/d5cp03677a","url":null,"abstract":"This study investigates the mechanism of Wacker-type oxidation of olefins mediated by the Pd-Quinox catalyst, which incorporates an electronically asymmetric quinoline-2-oxazoline (Quinox) ligand, utilizing density functional theory (DFT) calculations. The results demonstrate that oxidation proceeds via syn-peroxypalladation, followed by ring expansion and a 1,2-hydride shift, which is in agreement with the experimental results reported earlier. The 1,2-hydride shift is identified as the rate-limiting step. To evaluate the effects of ligand modification, a series of Pd(II) catalysts bearing Quinox ligands with various substituents on the quinoline moiety is examined. Furthermore, a series of para-substituted styrene derivatives is employed to examine the effects of substrate variation. We also investigate the effect of the electronic asymmetry of Quinox, pyridyl oxazoline (Pyrox), 2-(pyridin-2-yl)benzoxazole (PBO), and imidazolin-2-imine (AmIm) ligands on the stability of key catalytic intermediates in palladium-catalyzed Wacker-type oxidation, utilizing DFT and natural bond orbital (NBO) analysis. The findings indicate that these ligands influence the overall reaction pathway by controlling the arrangement of reactants on the metal center within the catalytic intermediates. The Pyrox ligand displays behavior similar to that of Quinox, whereas the AmIm ligand exhibits a stronger σ-donating and π-accepting character compared to the structurally related β-diketiminate (BDK) ligands. A detailed structural analysis of the optimized geometries of intermediates with these ligands, along with an in-depth discussion of second-order perturbation energies associated with various donor–acceptor interaction is presented.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"4 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203135","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

Strain induced half-metallic ferromagnetism and large anomalous Hall effect in Fe 2 CrGe fe2crge中应变诱导的半金属铁磁性和大反常霍尔效应

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp02785c

Mainak Dey Sarkar, Palash Nath, Debnarayan Jana, Dirtha Sanyal

{"title":"Strain induced half-metallic ferromagnetism and large anomalous Hall effect in Fe 2 CrGe","authors":"Mainak Dey Sarkar, Palash Nath, Debnarayan Jana, Dirtha Sanyal","doi":"10.1039/d5cp02785c","DOIUrl":"https://doi.org/10.1039/d5cp02785c","url":null,"abstract":"The fascinating topological features of magnetic topological semimetals (TSMs) with broken time-reversal symmetry have attracted a lot of interest in condensed matter physics in recent years. The inherent complexity of magnetism, however, causes the research of magnetic topological phases to lag behind. In this manuscript, we report a thorough investigation of the interplay between magnetism and topology of the full Heusler compound Fe 2 CrGe, employing density functional theory calculations. The ground state of Fe 2 CrGe is in an antiferromagnetic (AFM) metallic state, which, upon applying uniaxial strain, undergoes a magnetic phase transition to a half-metallic ferromagnet (HMF) state. Both compressive and tensile strains have been applied up to 3%, and the robustness of the half-metallic nature has been observed. The Curie temperature of the FM state is estimated by Monte Carlo simulations of the Ising model. We also analyzed the band topology of the strained system and have identified gapped nodal lines and symmetry-protected Weyl points (WPs) close to E F in the presence of spin-orbit coupling (SOC) and finite magnetization. The simultaneous existence of gapped nodal lines and symmetry-protected WPs gives rise to a strong Berry curvature (BC) distribution, which in turn generates significant intrinsic anomalous Hall conductivity (AHC). The strain-induced HMF nature and non-zero AHC make the Heusler alloy Fe 2 CrGe a promising contender for topological spintronics device applications and can also be used as a strain-controlled Hall-switch.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"99 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203106","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

Simulation of Radiation Damage on [M(COD)Cl]2 using Density Functional Theory 密度泛函理论对[M(COD)Cl]2辐射损伤的模拟

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp03310a

Nathalie Kanchena Fernando, Nayera Ahmed, Katherine Milton, Claire A. Murray, Anna Regoutz, Laura E. Ratcliff

{"title":"Simulation of Radiation Damage on [M(COD)Cl]2 using Density Functional Theory","authors":"Nathalie Kanchena Fernando, Nayera Ahmed, Katherine Milton, Claire A. Murray, Anna Regoutz, Laura E. Ratcliff","doi":"10.1039/d5cp03310a","DOIUrl":"https://doi.org/10.1039/d5cp03310a","url":null,"abstract":"Theoretical calculations of materials have in recent years shown promise in facilitating the analysis of convoluted experimental data. This is particularly invaluable in complex systems or for materials subject to certain environmental conditions, such as those exposed to X-ray radiation during routine characterisation. Despite the clear benefit in this use case to shed further light on intermolecular damage processes, the use of theory to study radiation damage of samples is still not commonplace, with very few studies in existing literature. In this paper, we demonstrate the potential of density functional theory for modelling the electronic structure of two industrially important organometallic systems of the formula [M(COD)Cl]<small><sub>2</sub></small> where M=Ir/Rh and COD=1,5-cyclooctadiene, which are subject to X-ray irradiation via X-ray Diffraction and X-ray Photoelectron Spectroscopy. Our approach allows calculated spectra to be compared directly to experimental data, in this case, the X-ray photoelectron valence band spectra, enabling the valuable correlation of individual atomic states to the electronic structure.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"47 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203145","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

Electronic Energy Levels of Aqueous Hydroxyl Species 羟基的电子能级

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp02299a

Francesco Ambrosio, Wei Chen, Alfredo Pasquarello

{"title":"Electronic Energy Levels of Aqueous Hydroxyl Species","authors":"Francesco Ambrosio, Wei Chen, Alfredo Pasquarello","doi":"10.1039/d5cp02299a","DOIUrl":"https://doi.org/10.1039/d5cp02299a","url":null,"abstract":"We study the structural and electronic properties of the aqueous hydroxyl species in the negatively charged and neutral states employing ab initio molecular dynamics (MD) simulations and advanced electronic structure calculations at the hybrid functional and many-body perturbation theory levels of theory. We first investigate the microsolvation of the solutes ensuing from MD, which show that the long discussed hemibond for the radical species does not form. The analysis of the electronic structure of the two states of the solvated species indicates the presence of in-gap localized states in both cases. Both structural and electronic features can be captured provided the self-interaction error of density functional theory is properly treated. Next, we calculate the electronic energy levels, namely the vertical and adiabatic redox potentials of the OH−/OH• couple, through thermodynamic integration within the grand-canonical formulation of solutes. We demonstrate that properly describing the valence band edge of liquid water and accurately accounting for electrostatic finite-size effects associated with periodic supercells with built-in ionic polarization are fundamental to achieve reliable redox levels. The calculated energy levels at the hybrid-functonal and quasiparticle self-consistent GW level of theory are found to be in excellent agreement with the experiment, thus allowing us to provide reliable estimates for the solvent reorganization upon charge transfer.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"99 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203658","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

The heat distribution of harmonically trapped single particles in active viscoelastic media 活跃粘弹性介质中单粒子谐波捕获的热分布

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI: 10.1039/d5cp02894a

Binny J. Cherayil

引用次数: 0