Physical Chemistry Chemical Physics最新文献_第10页

A theoretical investigation of heavy atom and oxidation effects in MR-TADF emitters for OLEDs: a combined DFT, double hybrid DFT, CCSD, and QM/MM approaches†

IF 2.9 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-21 DOI: 10.1039/D5CP00033E

Singaravel Nathiya, Murugesan Panneerselvam and Luciano T. Costa

{"title":"A theoretical investigation of heavy atom and oxidation effects in MR-TADF emitters for OLEDs: a combined DFT, double hybrid DFT, CCSD, and QM/MM approaches†","authors":"Singaravel Nathiya, Murugesan Panneerselvam and Luciano T. Costa","doi":"10.1039/D5CP00033E","DOIUrl":"10.1039/D5CP00033E","url":null,"abstract":"The emerging multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters with organoboron and nitrogen cores highlight their significance in OLEDs. However, their efficiency is challenged by slower rate constants in the reverse intersystem crossing (kRISC) process compared to conventional TADF emitters. The study entails an in-depth analysis focused on gaining a better understanding of the photophysical properties of MR-TADF emitters. Using DFT and TD-DFT analyses, 48 MR-TADF molecules are studied, incorporating heavy atoms such as sulfur and selenium, and their subsequent oxidation, and peripheral donors such as carbazole (Cz), tert-butyl-carbazole (tCz), diphenylacridine (DPAC), and dimethylacridine (DMAC) into organo boron and nitrogen-embedded systems. Moreover, the QM/MM approach was utilized to examine the excited state properties in the crystal phase. A comprehensive assessment of this molecular framework reveals that integrating heavy atoms and donors into MR-TADF molecules results in significant enhancements in ΔEST, larger SOC, and higher-order radiative (108 s−1) rates, leading to faster kISC (∼108 s−1) and kRISC (∼106 s−1) rates. Based on key criteria, eight potential molecules were selected and their excited-state properties were precisely analyzed using double-hybrid density functionals including B2PLYP and PBE0-2, along with highly correlated wave function STEOM-DLPNO-CCSD.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 14","pages":" 7265-7278"},"PeriodicalIF":2.9,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666447","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

Theoretical Prediction of Cluster Configuration Transition and Electro-Optical Properties of YP Defects in KH2PO4

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-20 DOI: 10.1039/d5cp00091b

Xu Lu, Tingyu Liu, Wei Hong, Huifang Li, Jianghai Wang

{"title":"Theoretical Prediction of Cluster Configuration Transition and Electro-Optical Properties of YP Defects in KH2PO4","authors":"Xu Lu, Tingyu Liu, Wei Hong, Huifang Li, Jianghai Wang","doi":"10.1039/d5cp00091b","DOIUrl":"https://doi.org/10.1039/d5cp00091b","url":null,"abstract":"The corrected defect formation energies, crystal structures, electronic behaviors, and optical properties of YP isolated defects and defect clusters YP+VO were studied using density functional theory. The results indicate that configuration transitions of point defects and cluster defects are encouraged under different oxygen partial pressures. Unlike Fe3+ or Cr3+, the defect formation energy of the YP defect center compensation by the nearest-neighbor VO is the lowest, suggesting that under oxygen-poor conditions, the defect cluster of YP defect composed of the nearest-neighbor O vacancy may be the main type of Yttrium-like trivalent rare earth metal atomic impurities in the crystal. Electronic behaviors show that the stronger coupling strength between the rare-earth metal Y and O and the bonding between H and O are the main reasons for the different ease of formation of different defect cluster structures. Thus, the interatomic interactions between the [YP+VO] cluster and isolated defect were analyzed, and an attempt was made to explain certain experimental phenomena. Finally, their optical properties were calculated, and the more pronounced defect levels and larger Stokes redshift indicate that cluster structures have a greater impact on the thermodynamic absorption of the crystal. New understanding has been given to the effects of laser pre-treatment on KDP crystals. This suggests that an oxygen-rich atmosphere may improve the LIDT of KDP crystals containing trivalent rare-earth metal impurities, providing a theoretical basis for enhancing the optical properties of the crystal.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"61 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660988","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

Additive-assisted oriented growth of cobalt oxide : controlled morphology and enhanced supercapacitor performance

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-20 DOI: 10.1039/d4cp03874f

Radhika S. Desai, Vinayak S. Jadhav, Sidharth R. Pardeshi, Pramod S Patil, Mohammad Rafe Hatshan, Yedluri Anil Kumar, Dhanaji S Dalavi

{"title":"Additive-assisted oriented growth of cobalt oxide : controlled morphology and enhanced supercapacitor performance","authors":"Radhika S. Desai, Vinayak S. Jadhav, Sidharth R. Pardeshi, Pramod S Patil, Mohammad Rafe Hatshan, Yedluri Anil Kumar, Dhanaji S Dalavi","doi":"10.1039/d4cp03874f","DOIUrl":"https://doi.org/10.1039/d4cp03874f","url":null,"abstract":"This research investigates the supercapacitor properties of cobalt oxide (Co₃O₄) thin films enhanced by five different additives: urea, ammonium chloride (NH₄Cl), ammonium hydroxide (NH₄OH), ammonium fluoride (NH₄F), and hexamethylenetetramine (HMT). The thin films are synthesized using a double hydrothermal approach on stainless steel substrates. Morphological and XRD analyses reveal well-separated Co₃O₄ nanowires stacked together, with diameters ranging from 10 to 34 nm and an average crystallite size between 19 to 23 nm. The additives serve as complexing agents, influencing the pH of the solution and facilitating the formation of cobalt-containing complexes, thereby promoting the uniform growth of Co₃O₄. Notably, the C-HMT nanowires exhibit superior supercapacitive performance, achieving a specific capacitance of 468.68 F g⁻¹ at a scan rate of 5 mV s⁻¹ and an impressive retention rate of 98.31% after 10,000 cycles at a scan rate of 100 mV s⁻¹. Additionally, a symmetric device composed of two C-HMT electrodes is developed, demonstrating practical application by effectively illuminating five parallel-connected LEDs for approximately 20 seconds. In conclusion, this study presents a pioneering application of C-HMT as a symmetric supercapacitor, showcasing significant advancements in performance for future flexible energy storage devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"14 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660955","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 interface hydrophilic-hydrophobic integration of fluorinated defective graphene towards biomedical applications

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-20 DOI: 10.1039/d5cp00075k

Jiawen Wang, Yi Yu, Huilong Dong, Yujin Ji, Weihua Ning, Youyong Li

{"title":"The interface hydrophilic-hydrophobic integration of fluorinated defective graphene towards biomedical applications","authors":"Jiawen Wang, Yi Yu, Huilong Dong, Yujin Ji, Weihua Ning, Youyong Li","doi":"10.1039/d5cp00075k","DOIUrl":"https://doi.org/10.1039/d5cp00075k","url":null,"abstract":"In biomedical fields, rational design of novel two-dimensional (2D) biomedical nanomaterials aims to precisely manipulate biomolecules, including efficient capture, structural-functional transformation, directional movement, and self-assembly. In this work, we innovatively proposed new graphene nanosheets and selected two representative proteins to explore their binding mechanisms, structural-functional transformation of proteins, and biological effects of the materials. Fluorinated defective graphene (FDG) exhibited highly efficient capture and structural-functional transformation for receptor binding domain (RBD), and we observed its collapse phenomenon in 2D materials firstly. For Main protease (Mpro), FDG achieved a perfect balance between efficient capture, immobilization, and structural disruption. Further studies showed that fluorination on oxygen-containing defects graphene significantly enhanced differences in water distribution, hydrophilicity, hydrophobicity, charge distribution, and hydrogen bond network on the material surface. This allowed amino acids to be confined to specific areas, achieving efficient capture, and directional movement. Additionally, the adsorption behavior and interaction strength of peptides and deoxynucleotides on FDG further validated the possibility of self-assembly. In summary, we highlight FDG as an excellent biomedical material with hydrophilic-hydrophobic integration.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"18 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660835","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

Mechanisms and dynamics of halophilic reaction between CH2CN- and CCl4

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-20 DOI: 10.1039/d5cp00105f

Siddharth Dutta, Sayoni Mitra, Upakarasamy Lourderaj

{"title":"Mechanisms and dynamics of halophilic reaction between CH2CN- and CCl4","authors":"Siddharth Dutta, Sayoni Mitra, Upakarasamy Lourderaj","doi":"10.1039/d5cp00105f","DOIUrl":"https://doi.org/10.1039/d5cp00105f","url":null,"abstract":"In gas phase experiments [J. Am. Soc. Mass Spectrom., 2005, 16, 2045], the reaction of the CH2CN- ion with CCl4 was observed to proceed predominantly via a halophilic reaction, where the nucleophile attacks a Cl atom, displacing the CCl3- ion, along with minor products from SN2 reactions and H/Cl exchange. In this study, the energetics of the three reaction pathways were investigated using DFT, MP2, and DLPNO-CCSD(T) methods. The B3LYP/6-311++G** level of theory accurately described the reaction pathways compared to the DLPNO-CCSD(T)/CBS benchmark while remaining computationally efficient. At the B3LYP/6-311++G** level, the halophilic pathway was found to be barrierless and energetically favorable, whereas the SN2 pathway exhibited an energy barrier of 4.34 kcal/mol relative to the reactants. The H/Cl exchange reaction is proposed to occur through sequential steps: an initial halophilic pathway followed by proton transfer, due to the high energy barrier of 11.71 kcal/mol for the direct reaction. The reaction dynamics, investigated through bimolecular ab initio trajectory simulations at the B3LYP/6-311++G** level, revealed the formation of major halophilic products, consistent with experimental findings. Additionally, the dynamics of the SN2 reaction were explored by analyzing the post-transition state trajectories.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"90 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660991","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

Slide and twist: manipulating polarization in multilayer hexagonal boron–nitride

IF 2.9 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-20 DOI: 10.1039/D5CP00375J

Sanber Vizcaya, Felipe Pérez Riffo, Juan M. Florez and Eric Suárez Morell

{"title":"Slide and twist: manipulating polarization in multilayer hexagonal boron–nitride","authors":"Sanber Vizcaya, Felipe Pérez Riffo, Juan M. Florez and Eric Suárez Morell","doi":"10.1039/D5CP00375J","DOIUrl":"10.1039/D5CP00375J","url":null,"abstract":"This study explores the world of across-layer sliding ferroelectricity in multilayer hexagonal boron nitride (hBN), aiming to control out-of-plane polarization. By investigating the effects of sliding single or dual layers in various hBN stacking configurations, we uncover methods for reversing polarization with energy barriers between 5 and 30 meV per f.u., making these methods experimentally viable. Our results show that single-interface sliding is more energetically favorable, with lower barriers compared to multiple interfaces. Certain pathways reveal stable polarization plateaus, where polarization remains constant during specific sliding phases, promising robust polarization control. Moreover, rotated multilayer structures maintain consistent net out-of-plane polarization across different rotation angles. In trilayer ABT structures, rotating the top layer and sliding the bottom layer can reverse polarization, expanding device design possibilities. While the primary focus is on hBN, similar phenomena in hGaN suggest broader applicability for this class of polar materials. The identified energy barriers support the feasibility of fabricating devices based on these multilayer structures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 14","pages":" 7189-7198"},"PeriodicalIF":2.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660954","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

High initial conductivity and oxidation resistance of copper nanowire films via depositing oxalic acid†

IF 2.9 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-20 DOI: 10.1039/D4CP04429K

Weiqiang Yuan, Xingzhong Zhu, Jizhe Zhang, Juan Xu, Yuhao Zhang, Junyao Cai, Ning Peng and Caixia Kan

{"title":"High initial conductivity and oxidation resistance of copper nanowire films via depositing oxalic acid†","authors":"Weiqiang Yuan, Xingzhong Zhu, Jizhe Zhang, Juan Xu, Yuhao Zhang, Junyao Cai, Ning Peng and Caixia Kan","doi":"10.1039/D4CP04429K","DOIUrl":"10.1039/D4CP04429K","url":null,"abstract":"Transparent conductive films based on copper nanowires (Cu NWs) have attracted extensive attention due to their cost-effectiveness. However, the inferior conductivity of Cu NWs compared to silver nanowires (Ag NWs) and the significant room temperature oxidation behavior have limited their widespread application and versatility. In this study, we present OA–Cu NW flexible transparent conductive films (FTCFs), which exhibit higher initial electrical performance and room temperature oxidation resistance. Initially, we synthesized high-purity Cu NWs and established a uniformly distributed Cu NW network on a PET substrate. Subsequently, post-treatment was carried out using a 0.1 M oxalic acid (OA) solution to immobilize oxalic acid on the Cu NWs. The resulting OA–Cu NW FTCFs show improved electrical properties compared to the original Cu NW FTCFs, with an optimal enhancement of 25%. The film demonstrated excellent room temperature oxidation resistance, showing minimal sheet resistance growth after 70 days of air exposure. Furthermore, the OA–Cu NW FTCFs exhibited good flexibility, as indicated by minimal changes in optoelectronic performance after a rigorous bend test of 10 000 cycles. The OA treatment not only effectively enhanced the performance of Cu NW FTCFs, but also circumvented high energy consumption and the selection of rare metal materials, thereby reducing the overall cost. As a result, the potential for large-scale production and application of Cu NW films is enhanced.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 14","pages":" 7177-7188"},"PeriodicalIF":2.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660987","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

Parity Violation Effects on the Electric Field Gradient

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-20 DOI: 10.1039/d4cp04840g

Juan José Aucar, Alejandro Fabián Maldonado

引用次数: 0

Machine learning assisted approximation of descriptors (CO and OH) binding energy on Cu-based bimetallic alloys†

IF 2.9 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-20 DOI: 10.1039/D4CP04887C

Pallavi Dandekar, Aditya Singh Ambesh, Tuhin Suvra Khan and Shelaka Gupta

{"title":"Machine learning assisted approximation of descriptors (CO and OH) binding energy on Cu-based bimetallic alloys†","authors":"Pallavi Dandekar, Aditya Singh Ambesh, Tuhin Suvra Khan and Shelaka Gupta","doi":"10.1039/D4CP04887C","DOIUrl":"10.1039/D4CP04887C","url":null,"abstract":"Data driven machine learning (ML) based methods have the potential to significantly reduce the computational as well as experimental cost for the rapid and high-throughput screening of catalyst materials using binding energy as a descriptor. In this study, a set of eight widely used ML models classified as linear, kernel and tree-based ensemble models were evaluated to predict the binding energy of catalytic descriptors (CO* and OH*) on (111)-terminated Cu3M alloy surfaces using the readily available metal properties in the periodic table as features. Among all the models tested, the extreme gradient boosting regressor (xGBR) model showed the best performance with the root mean square errors (RMSEs) of 0.091 eV and 0.196 eV for CO and OH binding energy predictions on (111)-terminated A3B alloy surfaces. Moreover, the xGBR model gave the highest R2 scores of 0.970 and 0.890 for CO and OH binding energies. The time taken by the ML predictions for 25 000 fits for each model was varied between 5 and 60 min on a 6 core and 8 GB RAM laptop, which was very negligible as compared to DFT calculations. Our ML model showed remarkable performance for accurately predicting the CO and OH binding energies on a (111)-terminated Cu3M alloy with a mean absolute error (MAE) of 0.02 to 0.03 eV compared to DFT calculated values. The ML predicted binding energies can be further used with an ab initio microkinetic model (MKM) to efficiently screen A3B-type bimetallic alloys for the formic acid decomposition reaction.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 14","pages":" 7151-7168"},"PeriodicalIF":2.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cp/d4cp04887c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660990","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

Assessment of the Piris natural orbital functionals on transition metal dihydrides

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-03-20 DOI: 10.1039/d4cp04010d

Lizeth Franco, Roberto Rojas-Hernández, Ivan Alejandro Bonfil-Rivera, Emilio Orgaz, Jorge M. del Campo

{"title":"Assessment of the Piris natural orbital functionals on transition metal dihydrides","authors":"Lizeth Franco, Roberto Rojas-Hernández, Ivan Alejandro Bonfil-Rivera, Emilio Orgaz, Jorge M. del Campo","doi":"10.1039/d4cp04010d","DOIUrl":"https://doi.org/10.1039/d4cp04010d","url":null,"abstract":"Transition metal dihydrides can be seen as a starting point for the study of the interaction between H2 and d-metal ligands that are widely recognized as challenging molecules for electronic structure methods due to their possible multireference character and electronic correlation effects. The performance of different proposed Piris natural orbital functionals (PNOFs), such as PNOF5, PNOF7, and the global functional (GNOF), in predicting the formation of 3d-transition metal dihydrides was evaluated. A comparison between the results of the PNOFs and several state-of-the-art techniques has been carried out. It was found that all PNOF methods are consistent when static correlation effects are negligible. In particular, PNOF7 demonstrated the most accurate ratio for predicting the formation of the dihydrides and energy profiles, according to multireference methods. On the other hand, although the GNOF method successfully predicts the equilibrium geometries, it overstabilizes systems with high static correlation, such as low multiplicity dihydrides of intermediate 3d-series transition metals. As a whole, they indicate activation of the H2 bond for all metals and also the formation of dihydrides, except for Co, Cu and Zn.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"9 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660986","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