Physical Chemistry Chemical Physics最新文献

{"title":"Co-immobilization of rhodium catalyst and LDH on carbon electrode by covalent graft strategy for electrosynthesis L-lactate in bipolar electrochemistry","authors":"Chunhua Zhang, Bowen Li, Xiang Gao, Wei Xiao, Mingfang Chen, Qilong Bian","doi":"10.1039/d5cp02222c","DOIUrl":"https://doi.org/10.1039/d5cp02222c","url":null,"abstract":"This work demonstrates a wireless electroenzymatic platform using carbon microsphere electrodes co-immobilized with a rhodium catalyst and lactate dehydrogenase (LDH) for integrated NADH regeneration and pyruvate-to-L-lactate conversion in a bipolar electrochemical system. The 3D \"aggregate reactor\" architecture, functionalized via diazonium grafting, Rh coordination, and covalent enzyme coupling, enables spatial coupling of cofactor recycling and biocatalysis, while HPLC revealed a L-lactate production rate of 0.04 mM cm-2 h⁻¹ under 12.5 V cm⁻¹ with a plenty of carbon beads attributed to enhanced mass transport. This wireless, scalable design eliminates wiring constraints and offers modular adaptability for sustainable synthesis of chiral chemicals.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"12 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719440","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":"UV-VUV absorption spectroscopy and photodissociation dynamics of n-propylamine","authors":"Neha Sharma, Aparna Shastri, Asim Kumar Das, Vandana Rawat, Rajasekhar Naga Balabhadrapatruni","doi":"10.1039/d5cp01479d","DOIUrl":"https://doi.org/10.1039/d5cp01479d","url":null,"abstract":"We report for the first time, the UV-VUV absorption spectrum of n-propylamine in the wavenumber range 40,000 to 75,000 cm-1 (5.0–9.3 eV) using synchrotron radiation. A detailed spectral analysis is performed with the help of TDDFT based calculations. All the electronic excited states of n-propylamine are found to be Rydberg in nature, quantum defect analysis is used to assign Rydberg series converging to the first IP of n-propylamine. Theoretical simulation of the electronic absorption spectrum is done including vertical excited states of all five stable conformers which reproduces quite accurately, the observed intensity profile of the room temperature absorption spectrum. Vibrational structure associated with the 3s, 3p and 4s transitions clearly shows a dominant excitation of the NH2 wagging mode implying a transformation of the NH2 group from pyramidal structure in the ground state to planar in the excited state. Further, relative intensities of vibronic bands in the 3s Rydberg are simulated using Franck-Condon factor calculations and show overall good agreement with experiment. Relaxed potential energy scans across dihedral angles using DFT method reveal two stable conformers in the cationic ground state in contrast to five in the neutral ground state, which may have important implications in astrophysical studies. Absorption cross section data in the UV region, a valuable input in atmospheric modelling is used to simulate the variation of photolysis rate and lifetime of n-propylamine with terrestrial altitude. Additionally, detailed potential energy scans of excited states, both constrained and relaxed, along each of the possible bond cleavage channels are presented, revealing new insights into the photodissociation dynamics of the molecule.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"69 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719433","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":"Linear–Cyclic Isomer Competition in Protonated Ethanol–Methanol Clusters Probed by Infrared Spectroscopy and Deep Learning Structural and Dynamical Simulations","authors":"Po-Jen Hsu, Atsuya Mizuide, Jer-Lai Kuo, Asuka Fujii","doi":"10.1039/d5cp02353j","DOIUrl":"https://doi.org/10.1039/d5cp02353j","url":null,"abstract":"The competition between linear and cyclic isomer structures in the protonated ethanol tetramer has been investigated using spectroscopic and theoretical approaches. Infrared spectroscopy of protonated ethanol–methanol mixed tetramers, cooled by the inert gas tagging technique, revealed a significant dependence of the isomer structure competition on the mixing ratio and the tag species. To investigate isomer competition, structure searches were performed using the parallelized Basin-Hopping algorithm with neural network potentials that approximate the accuracy of density functional theory. Spectral simulations were conducted via harmonic vibrational analysis of key stable isomers using density functional theory and power spectral density calculations from molecular dynamics trajectories based on the neural network potentials. Comparison with experimental data reveals that the global minimum of the protonated ethanol tetramer is a linear structure. Additionally, the tag species significantly influences the relative stability of linear and cyclic isomers, as well as the isomerization barrier between these two structures.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"23 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719435","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":"Optical gaps of F-center defects in LiF using many-body methods","authors":"Ritaj Tyagi, Abhisek Ghosal, Vamsee K Voora","doi":"10.1039/d5cp02179k","DOIUrl":"https://doi.org/10.1039/d5cp02179k","url":null,"abstract":"<em>F</em>-center defects, occuring in technologically important wide-bandgap solids, influence the properties of the parent material. Their experimental characterization can be challenging due to low concentrations and spectral broadening. Modeling of these defects poses computational challenges due to their aperiodic nature, lattice distortion effects, and the need to describe many-body polarization effects induced by the surrounding environment. Here, we study bulk and surface <em>F</em>-center defects in LiF by combining random phase approximation (RPA) based potentials with periodic electrostatic embedding. We evaluate the accuracy of computationally efficient potentials such as single-pole exchange-correlation (1p-XC) and static-Coulomb hole screened exchange (st-COHSEX), and find the former to be suitable for bulk and surface <em>F</em>-center defects. For the commonly studied case of bulk <em>F</em>-centers, the 1p-XC approach predicts an optical gap (Δ<small>_og</small>) of 5.24 eV, closely matching high-level quantum chemistry methods like CASPT2 (Δ<small>_og</small>=5.31 eV) and within 0.16 eV of experimental absorption maximum. For surface <em>F</em>-centers, which are largely unexplored, we find a significantly lower optical gap of 1.85 eV. The smaller gap arises from reduced confinement effects and significantly larger lattice relaxation induced by surface <em>F</em>-center defect compared to bulk. On the other hand, the polarization corrections to the optical gaps are similar for both cases.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"50 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719437","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":"Influence of hydration, hydroxylation, and doping of TiO2(110) on the adsorption and decomposition of sarin. A density functional theory investigation","authors":"Yenny Cardona Quintero, Ramanathan Nagarajan","doi":"10.1039/d5cp01092f","DOIUrl":"https://doi.org/10.1039/d5cp01092f","url":null,"abstract":"Metal oxides are promising candidates for the adsorption and decomposition of chemical warfare agents (CWA) and can be the foundations of novel CWA destruction technologies. In this work, we use density functional theory (DFT) to explore how dry, wet and doped states of the metal oxide TiO2(110), influence the adsorption and chemical dissociation of the nerve agent, sarin. The DFT calculations show that the dissociative adsorption of sarin is more energetically favored than the molecular adsorption for all dry, wet and doped states of TiO2(110). The calculated energy barrier for the adsorption of sarin on dry TiO2(110) showed that sarin is initially adsorbed with a molecular configuration, followed by the dissociative process. For the adsorption of sarin on wet TiO2, under both hydrated and hydroxylated states, the 0.5 H2O monolayer (ML) showed the lowest adsorption energy compared to the dry and other wetness levels explored. Finally, the adsorption of sarin on TiO2(110) doped with Hf showed lower adsorption energy and higher charge transfer compared with TiO2(110) doped with Zr and Ge, as well as the undoped systems. These results demonstrate how hydration, hydroxylation, and doping of TiO2(110) significantly influence the adsorption and decomposition of sarin on this metal oxide.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"110 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719431","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":"Possible Transformation between Half-Metallic and Metallic States of Multiferroic MnGaSSe2 Monolayers","authors":"Zhiwen He, Shu Wang, Xue Rui, Jun Zhu, Yi Sun, Jinlian Lu, Xueke Yu, Xiuyun Zhang","doi":"10.1039/d5cp01741f","DOIUrl":"https://doi.org/10.1039/d5cp01741f","url":null,"abstract":"Multiferroic (MF) materials, exhibiting magnetic-electronic coupling properties, hold transformative potential for low-power spintronic devices. In this work, we investigate the structural, electronic and magnetic properties of a multiferroic MnGaSSe2 monolayer using first-principles calculations. Our results show that the O–phase MnGaSSe2 (O–MnGaSSe2) monolayer exhibits a ferromagnetic (FM) semimetallic character with long-range magnetic order, while the T–phase MnGaSSe2 (T–MnGaSSe2) monolayer adopts an FM metallic ground state. The super-exchange interactions mediated by the Se–Mn–S atomic chains give rise to strong intralayer FM coupling, resulting in Curie temperatures (TCs) of 159 K and 75 K for O–MnGaSSe2 and T–MnGaSSe2, respectively. Moreover, the FM half-metallic (HM) properties of O–MnGaSSe2 are robust under biaxial strain engineering, while T–MnGaSSe2 undergoes a reversible phase transition from FM metal to antiferromagnetism (AFM) metal under 4% compressive strain. These findings establish a design strategy for intrinsic MF materials with coupled FM and ferroelectric (FE) properties.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"129 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719441","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":"Observation of Competing Magnetic Phases, Mechanical Stability, Electronic Structure, Magnetism, and Remarkable Thermoelectric Aspects of the Ba2GdRuO6","authors":"Usman Saeed, Shehla Yasmeen, A. Ibrahim, Safdar Nazir","doi":"10.1039/d5cp02595h","DOIUrl":"https://doi.org/10.1039/d5cp02595h","url":null,"abstract":"The Ba2 GdRuO6 (BGRO) double perovskite oxide (DPO) demonstrates intriguing behavior, arising from competing antiferromagnetic (AFM) and ferrimagnetic (FiM) phases. Under the GGA+U+SOC scheme, the system exhibits an AFM ground state with a very small energy difference of −11.39 meV with FiM one. In contrast, spin modeling reveals significant magnetic frustrations along the z-axis and favors the FiM phase. Also, the magnetic phase transition discloses a Curie temperature (T_C) of 60 K. Additionally, magnetization measurements also affirm the FiM nature which lost saturation at higher temperatures, indicating a transition from FiM to paramagnetic above T_C. The electronic structure displays the semiconductor nature owing to a direct energy gap of 1.04/0.89 eV in the AFM/FiM state. The determined spin moments on the Gd(1-2)/Ru(1-2) and Gd(3-4)/Ru(3-4) ions are +6.9/+2.0 µB and −6.9/−2.0 µB in the AFM SO, respectively, while they are +6.89/−2.0 on the Gd(1-4)/Ru(1-4) ion in the FiM one. It is found that, Gd3+ and Ru4+ ions lie in +3(4f ^7) and +4(4d^4) alence state with the electronic configurations of [ fx(x2 −3y2 ) ]↑0 ↓1 [ fy(3x2 −y2 ) ]↑0 ↓1 [ fz(x2 −y2 ) ]↑0 ↓1 [ fxyz ]↑0 ↓1 [ fxz2 ]↑0 ↓1 [ fyz2 ]↑0 ↓1 [ fz3 ]↑0 ↓1 and 3 ↑ t 1 ↓ e0 ↑ e0 ↓ with spin quantum number of 7/2 and 1, correspondingly. Furthermore, the mehanical stability of the material is validated by satisfying the Born stability criteria and the ductility (B/G= 5.19). Noticeably, the presence of a positive Cauchy presis determined by the Pugh’s ratio of 66.53 GPa further supports the ionic nature of the motif. Besides, the system illustrates a positive Seebeck coefficient, indicating holes as the dominant charge carriers with the highest of 279 µV/K at 400 K. Remarkably, system achieves a high figure of merit of 0.86 at 550 K even with the inclusion of lattice thermal conductivity as well as sustaining excellent thermoelectric performance, suggesting a strong potential for elevated temperature energy harvesting applications along with spintronics.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"46 2 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719577","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":"Recent advances in circularly polarized luminescence (CPL) of chiral boron difluoride complexes","authors":"Masahiro Ikeshita, Takashi Tsuno","doi":"10.1039/d5cp02366a","DOIUrl":"https://doi.org/10.1039/d5cp02366a","url":null,"abstract":"Circularly polarized luminescence (CPL) has emerged as an intrigung photophysical phenomenon with potential applications in optoelectronics, bioimaging, and anti-counterfeiting materials. Among various CPL-active molecules, chiral boron difluoride complexes have attracted considerable attention due to their structural versatility, tunable emission properties and high luminescence efficiencies. This review summarizes recent progress in the design, synthesis, and photophysical properties of chiral boron difluoride complexes exhibiting CPL. We highlight key structural motifs, including boron-dipyrromethenes (BODIPYs), boron β-diketonates and boranils that have been successfully employed to induce efficient CPL activity. Moreover, we discuss the relationships between molecular structure and CPL performance, the mechanisms underlying CPL generation, and emerging strategies to improve emission efficiency and chiroptical properties. Finally, future perspectives are outlined with an emphasis on the challenges and opportunities in developing next-generation CPL-active materials based on boron difluoride frameworks.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"19 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719439","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":"Injection Rate Control on Growth Direction in Chemical Gardens","authors":"Satoshi Nakata, Yujin Kubodera, Muneyuki Matsuo","doi":"10.1039/d5cp01908g","DOIUrl":"https://doi.org/10.1039/d5cp01908g","url":null,"abstract":"The spontaneous organization of inorganic structures holds potential for applications in biomimetic material design. In this study, tubular precipitation structures were produced by injecting an aqueous solution of copper chloride into an aqueous solution of sodium silicate within an upright Hele-Shaw cell. The direction of tube growth, either upward or lateral, depended on the injection rate. The mechanism for selecting growth direction and its bifurcation was examined in relation to factors such as injection rate, water penetration, and the density differences between the two reactive solutions. This investigation contributes to the understanding of controlled inorganic spontaneous organization. It paves the way for diverse and autonomous growth in response to their environmental conditions, akin to plant growth or vascular formation in living organisms.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"15 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719444","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":"Reaction Mechanism of Silylation of C−O Bonds in Alkyl Ethers over Supported Gold Catalysts: Experimental and Theoretical Investigations","authors":"Yunosuke Tsunesada, Tatsushi Ikeda, Koki Muraoka, Masafumi Doi, Hiroki Miura, Tetsuya Shishido, Akira Nakayama","doi":"10.1039/d5cp01973g","DOIUrl":"https://doi.org/10.1039/d5cp01973g","url":null,"abstract":"The reaction mechanism of <em>α</em>-Fe<small>₂</small>O<small>₃</small>-supported Au-catalyzed silylation of ether C(sp<small>³</small>)–O bonds by disilane is investigated using both experimental and computational approaches. The experimental study reveals that the ether activation is the rate-determining step in the silylation of C(sp<small>³</small>)–O bonds and that this reaction proceeds via the S<small>_H</small>2-type mechanism involving radical species. DFT calculations demonstrate that the Si–Si bond cleavage in disilane occurs at the interface between Au cluster and <em>α</em>-Fe<small>₂</small>O<small>₃</small> support with a low activation energy and that the subsequent attack by silyl radicals on the ether involves an energy barrier consistent with the experimental results. These investigations provide valuable insights into the unique reaction mechanism of ether C(sp<small>³</small>)–O bond activation, which could serve as a basis for the development of novel supported metal catalyst systems.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"52 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719432","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}