Physical Chemistry Chemical Physics最新文献_第10页

Infrared band ultra wideband metamaterial absorption device based on cylindrical multiscale resonator 基于圆柱形多尺度谐振器的红外波段超宽带超材料吸收装置

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-05 DOI: 10.1039/d5cp00968e

Jiao Wang, Qianju Song, Hua Yang, Chaojun Tang, Zao Yi, Jianguo Zhang

{"title":"Infrared band ultra wideband metamaterial absorption device based on cylindrical multiscale resonator","authors":"Jiao Wang, Qianju Song, Hua Yang, Chaojun Tang, Zao Yi, Jianguo Zhang","doi":"10.1039/d5cp00968e","DOIUrl":"https://doi.org/10.1039/d5cp00968e","url":null,"abstract":"Mid-infrared and far-infrared regions broadband absorption is of great significance in science and technology. In this paper, we put forward a mid-far infrared metamaterial absorber, and Finite-Difference Time-Domain simulation calculation shows that the absorption rate in the 6.73-16.65 μm band, with an average absorption rate of 96.01%. At the same time, although the absorption performance depends on the polarization state and the incidence angle, it shows the relative stability in a wide angle range. Using the FDTD electromagnetic field analysis visualize the electric and magnetic field intensity distributions within the absorber, it can be known that the resonance mode of the absorber has surface plasmon resonance (SPR), localized surface plasmon resonance (LSPR), and Fabry-Perot cavity resonance. Meanwhile, adjusting the absorption layer thickness and the periodic geometry parameters can optimize the absorption performance. In addition, different microstructures and different top materials also have an influence on the absorption rate of the absorber. The absorber has high practical value in thermoelectric devices, infrared imaging and thermal detection.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"17 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219107","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

Pronounced excitonic effects in two-dimensional fullerene-based monolayer materials† 二维富勒烯基单层材料的激子效应

IF 2.9 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-05 DOI: 10.1039/D5CP01203A

Ning Li, Tianqi Bao, Yang Zhao, Fan Zhang, Junfeng Zhang, Xue Jiang, Nikolai Cherenda, Weiwei Gao, Jijun Zhao and Yan Su

{"title":"Pronounced excitonic effects in two-dimensional fullerene-based monolayer materials†","authors":"Ning Li, Tianqi Bao, Yang Zhao, Fan Zhang, Junfeng Zhang, Xue Jiang, Nikolai Cherenda, Weiwei Gao, Jijun Zhao and Yan Su","doi":"10.1039/D5CP01203A","DOIUrl":"10.1039/D5CP01203A","url":null,"abstract":"Two-dimensional (2D) fullerene monolayer materials exhibit a wide range of unique properties, including pronounced excitonic effects with significant potential for optoelectronic applications. Here, we perform a comprehensive investigation of the quasiparticle (QP) and excitonic properties of the C20-2D monolayer using density functional theory (DFT) and many-body perturbation theory (MBPT) based on the GW approximation and Bethe–Salpeter equation (GW–BSE). Our calculations reveal substantial excitonic effects in the C20-2D monolayer, with an impressive exciton binding energy of 1.58 eV, a notable breakthrough compared to the 0.8 eV reported for the C60 monolayer. Embedding magnesium (Mg) into the C20-2D monolayer induces polarization effects and enhances dielectric screening, driving a transition of the lowest-energy excitons from the Frenkel to the Wannier type. This transition is accompanied by significant changes in both the intensity and range of optical absorption. These findings reveal the tunability of fullerene materials through embedding, offering insights for the development of next-generation optoelectronic devices.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 24","pages":" 12848-12857"},"PeriodicalIF":2.9,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219106","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

Mutation-induced rigidity in the Fyn SH2 domain enhances pY-binding affinity at the cost of peptide specificity† 突变诱导的Fyn SH2结构域刚性以牺牲肽特异性为代价增强py结合亲和力

IF 2.9 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-05 DOI: 10.1039/D5CP00015G

Li Deng, Yang Zou, Junbao Zhu, Lei Li and Yanting Wang

{"title":"Mutation-induced rigidity in the Fyn SH2 domain enhances pY-binding affinity at the cost of peptide specificity†","authors":"Li Deng, Yang Zou, Junbao Zhu, Lei Li and Yanting Wang","doi":"10.1039/D5CP00015G","DOIUrl":"10.1039/D5CP00015G","url":null,"abstract":"Interactions between SH2 domains and tyrosine-phosphorylated (pY) peptides are essential for cellular signaling. While structural studies have revealed how triple-point Fyn SH2 mutants achieve ultra-high pY-peptide affinity, the dynamic consequences of these mutations remain unexplored. In this study, we performed extensive all-atom molecular dynamics simulations on the isolated wild-type Fyn SH2 domain, its mutant, and their complexes with the pY-peptide (EPQpYEEIPIYL). Comparative analyses of these simulations provided dynamic insights into how mutations within the pY-binding pocket alter the interaction between Fyn SH2 domain and the pY-peptide. Our results demonstrate that the mutations significantly influence the dynamic stability of unstructured regions within the SH2 domain and the domain-peptide interface. Specifically, the mutations enhance the rigidity and stability of the pY-binding pocket, as well as the overall structural stability of the domain, including the central β-sheet and terminal regions. This increased rigidity in the mutant enhances interactions between the pY-binding pocket and pY but weakens the interaction with the peptide residue at the +3 position relative to pY, thereby compromising the specificity of the domain-peptide interaction. These findings highlight that the interaction between SH2 domains and pY-peptides is governed not only by the structural properties of the pY-binding pocket but also by the dynamic stability of the domain itself. This insight could guide the experimental design of SH2 domains engineered to recognize post-translational modifications with diverse characteristics.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 24","pages":" 13091-13102"},"PeriodicalIF":2.9,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219103","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

Switching of Circularly Polarised Luminescence in Perylene-Diimide-Based Chiral Liquid Crystals Induced by Electric Fields and Heating 电场和加热诱导苝-二亚胺基手性液晶圆偏振发光的开关

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-04 DOI: 10.1039/d5cp01592h

Daiya Suzuki, Seika Suzuki, Kosuke Kaneko, Tomonori Hanasaki, Motohiro Shizuma, Yoshitane Imai

{"title":"Switching of Circularly Polarised Luminescence in Perylene-Diimide-Based Chiral Liquid Crystals Induced by Electric Fields and Heating","authors":"Daiya Suzuki, Seika Suzuki, Kosuke Kaneko, Tomonori Hanasaki, Motohiro Shizuma, Yoshitane Imai","doi":"10.1039/d5cp01592h","DOIUrl":"https://doi.org/10.1039/d5cp01592h","url":null,"abstract":"Two pairs of chiral perylene-based luminescent materials, namely (R,R)/(S,S)-N,N’-bis(1-phenylethyl)perylene-3,4,9,10-tetracarboxylic diimide [(R,R)/(S,S)-BPP] and (R,R)/(S,S)-N,N’-bis(1-cyclohexylethyl)perylene-3,4,9,10-tetracarboxylic diimide [(R,R)/(S,S)-CPDI], were doped into a nematic liquid crystal with a low phase transition temperature, 4'-hexyl-4-biphenylcarbonitrile. The resultant luminescent chiral nematic liquid crystals (N*-LCs) exhibited a circularly polarised luminescence (CPL) stronger than that of chiral poly(methyl methacrylate)-based luminescent films containing BPP and CPDI. Both N*-LCs displayed reversible CPL property responses (CPL intensity and CPL sign inversion) upon the application of a direct-current (DC) electric field (due to a chiral nematic phase → nematic phase transition) and heating (due to a chiral nematic phase → isotropic phase transition). Thus, an on-off-on CPL system controlled by DC electric fields and thermal stimuli was constructed based on a transition from a uniformly aligned helical structure to another orientational arrangement. This work provides an effective strategy for the development of functional CPL devices based on CPL control via N*-LC exposure to DC electric fields or heat.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"7 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211443","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

Transformation of starphenes into amorphous graphene nanoribbons with attached carbon chains under electron irradiation† 电子辐照下starphenes向非晶碳链石墨烯纳米带的转变

IF 2.9 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-04 DOI: 10.1039/D5CP00507H

Alexander S. Sinitsa, Yulia G. Polynskaya, Yegor M. Kedalo, Andrey A. Knizhnik and Andrey M. Popov

{"title":"Transformation of starphenes into amorphous graphene nanoribbons with attached carbon chains under electron irradiation†","authors":"Alexander S. Sinitsa, Yulia G. Polynskaya, Yegor M. Kedalo, Andrey A. Knizhnik and Andrey M. Popov","doi":"10.1039/D5CP00507H","DOIUrl":"10.1039/D5CP00507H","url":null,"abstract":"Transformation of starphene molecules with four acene arms on a graphene substrate under electron irradiation is studied by molecular dynamics (MD) simulations using the CompuTEM algorithm. A set of various pure carbon molecules ranging from carbon propeller-like molecules with four long carbon atomic chains connected to the central polycyclic aromatic region to amorphous graphene nanoribbons with short attached chains are observed after hydrogen removal by electron impacts. A two stage atomistic mechanism is revealed for the transformation. The first stage is spontaneous breaking of bonds between zigzag atomic rows in starphene arms during hydrogen removal with formation of atomic carbon chains. The second stage is formation of new carbon–carbon bonds between neighboring chains that leads to an increase in the size of the central polycyclic region that survived the first stage. The kinetic electron energy in the range from 45 to 80 keV has negligible influence on the distribution of the obtained molecules. The performed DFT calculations confirm the revealed atomistic mechanism and the adequacy of the REBO-1990EVC-EH potential used in the MD simulations.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 24","pages":" 12729-12737"},"PeriodicalIF":2.9,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211445","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

Synthesis, photocatalytic application and future prospect of noble metals modified semiconductors fabricated via photodeposition 光沉积制备贵金属修饰半导体的合成、光催化应用及前景展望

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-04 DOI: 10.1039/d5cp01191d

Faqi Zhan, Jiahao Qi, Ruixin Li, Haiyan Zhao, Yisi Liu, Peiqing La

{"title":"Synthesis, photocatalytic application and future prospect of noble metals modified semiconductors fabricated via photodeposition","authors":"Faqi Zhan, Jiahao Qi, Ruixin Li, Haiyan Zhao, Yisi Liu, Peiqing La","doi":"10.1039/d5cp01191d","DOIUrl":"https://doi.org/10.1039/d5cp01191d","url":null,"abstract":"In recent years, the energy crisis and environmental pollution have become two major global challenges, necessitating the development of new clean energy sources and technologies to address these issues. Currently, photocatalytic technology has emerged as one of the most promising new technologies. Semiconductor photocatalytic technology mainly involves three processes: light absorption, separation and transport of photogenerated charges, and surface catalytic reactions. To overcome the drawbacks of poor light responsiveness and weak interfacial charge conductivity in traditional semiconductor photocatalysts, noble metals with surface plasma effects are commonly used to enhance semiconductor photocatalytic performance. Noble metals in the field of photocatalysis have the advantages of accelerating electron migration rates, preventing electron-hole pair recombination, and enhancing the utilization efficiency of photogenerated electrons. After modification with loaded noble metals, the photocatalytic efficiency of semiconductors is significantly enhanced. This paper reviews the synthesis and application of noble metals loaded via photochemical deposition in the field of photocatalysis, focusing on the preparation processes, structural characteristics, and their applications and mechanisms in photocatalytic water splitting, pollutant degradation, and CO2 reduction. Finally, the potential applications and prospects of photodeposition technology in noble metal recovery and extraction, single-atom catalyst preparation, biomedicine, and photocatalytic-assisted organic synthesis are proposed, which positively promote the development of photocatalysis field and the circular economy of noble metal resources.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"16 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211442","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

Estimating protein binding upon treatment with radionuclide ions 估计用放射性核素离子处理后蛋白质的结合

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-04 DOI: 10.1039/d5cp00299k

Ran Friedman

{"title":"Estimating protein binding upon treatment with radionuclide ions","authors":"Ran Friedman","doi":"10.1039/d5cp00299k","DOIUrl":"https://doi.org/10.1039/d5cp00299k","url":null,"abstract":"Several types of radioactive isotopes are used for cancer treatment. While most are embedded in chelating agents, 223Ra is given as RaCl2 salt and 90Y in microspherical particles. If ionic radionuclides are free, they have the potential to bind to proteins instead of their endogenous ions, interfere with their activity and be transported by them. In this study, a computational approach was used to estimate the binding affinities of Y3+ , Ra2+ and Pb2+ (207Pb is the decay product of 223Ra) to proteins, instead of their native cofactors Ca2+ and Mn2+ . Y3+ was found to bind strongly to proteins with the ability to replace Ca2+ and to some degree also Mn2+ . Ra2+ does not bind to the studied proteins but Pb2+ can replace Ca2+ in Ca2+ binding proteins. A recently identified coordination compound was found to be highly selective for 223Ra.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"8 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211441","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

Mechanistic insights into the thermodynamics and kinetics underlying the reductive decomposition of fluoroethylene and difluoroethylene carbonates for SEI formation in LIBs† 在lib中形成SEI的氟乙烯和二氟乙烯碳酸酯还原性分解的热力学和动力学机制的见解

IF 2.9 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-04 DOI: 10.1039/D5CP01285F

Ruru Song, Tairan Wang, Yiyang Pan, Cuili Zhang, Lang Wang, Shengbo Lu, Tracy Chenmin Liu, Shihan Qi, Weiguo Huang, Jingjing Liu, Guannan Zhu and Jun Fan

{"title":"Mechanistic insights into the thermodynamics and kinetics underlying the reductive decomposition of fluoroethylene and difluoroethylene carbonates for SEI formation in LIBs†","authors":"Ruru Song, Tairan Wang, Yiyang Pan, Cuili Zhang, Lang Wang, Shengbo Lu, Tracy Chenmin Liu, Shihan Qi, Weiguo Huang, Jingjing Liu, Guannan Zhu and Jun Fan","doi":"10.1039/D5CP01285F","DOIUrl":"10.1039/D5CP01285F","url":null,"abstract":"Fluoroethylene carbonate (FEC) and difluoroethylene carbonate (DFEC) are electrolyte additives that significantly influence the formation of the solid electrolyte interphase (SEI) during the initial cycling of lithium-ion batteries (LIBs). While FEC has been partially explored, the reductive decomposition mechanism of DFEC, particularly its kinetic and thermodynamic behaviour, remains poorly understood. In this work, we employ density functional theory (DFT) simulations to systematically investigate the thermodynamic (free energy, ΔG) and kinetic (free energy barrier, ΔG‡) parameters governing the reductive decomposition pathways of FEC and DFEC. The results indicate that both additives predominantly undergo direct two-electron reduction processes to form LiF and CO as the primary products. DFEC exhibits thermodynamic and kinetic behavior comparable to that of FEC. Notably, DFEC features a unique double-defluorination pathway that generates additional LiF, potentially enhancing SEI stability. Mayer bond order (MBO) and atomic dipole moment corrected Hirshfeld (ADCH) charge analyses further reveal that the Li+ coordination facilitates the defluorination process. These findings offer new insights into the decomposition of DFEC and confirm its ability to form LiF-rich SEI layers, highlighting DFEC as a promising electrolyte additive for stable and high-performance LIBs.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 24","pages":" 12711-12720"},"PeriodicalIF":2.9,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211248","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

Ion exchange: An essential piece in the fabrication of zeolite adsorbents 离子交换：在沸石吸附剂的制造中必不可少的一部分

IF 3.3 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-04 DOI: 10.1039/d5cp00894h

Chenxin Li, Tiesen Li, Qingyan Cui, Tinghai Wang, Chan Wang, Jiao Yang, Jie Shi, Xiaojun Bao, Yuanyuan Yue

{"title":"Ion exchange: An essential piece in the fabrication of zeolite adsorbents","authors":"Chenxin Li, Tiesen Li, Qingyan Cui, Tinghai Wang, Chan Wang, Jiao Yang, Jie Shi, Xiaojun Bao, Yuanyuan Yue","doi":"10.1039/d5cp00894h","DOIUrl":"https://doi.org/10.1039/d5cp00894h","url":null,"abstract":"Adsorptive separation, which relies on the size, polarity, and affinity of guest molecules, is an efficient, eco-friendly, and cost-effective method. Zeolite-based adsorbents, known for their uniform pore size and regenerability, have exhibited exceptional performance in many challenging adsorption processes, such as the separation of n-paraffin/i-paraffin and xylene isomers. Ion exchange, as an essential piece in the fabrication of zeolite-based adsorbents, significantly affects overall performance. In this review, we survey the recent key developments and issues within ion exchange research of zeolite-based adsorbents, including the solution pH, solution concentration, ion-exchange cycles, ion-exchange temperature, ion-exchange time, calcination temperature, and discuss the mechanisms of their influence on zeolite adsorption. This review also elaborates on the negative effects of improper ion exchange on incomplete cation exchange, cation migration, collapse of the zeolite structure, and blockage of zeolite pores. Other parameters that lack of research but have been proven to affect ion exchange are also mentioned. We hope to generate interest in the wider community and encourage others to make use of ion exchange in tackling challenges of adsorption separation science and engineering.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"5 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211440","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 challenging conformer assignment of proline methyl ester from rotational spectroscopy† 从旋转光谱研究脯氨酸甲酯具有挑战性的构象分配

IF 2.9 3区化学

Physical Chemistry Chemical Physics Pub Date : 2025-06-04 DOI: 10.1039/D5CP00898K

Dinesh Marasinghe, Michael J. Carrillo, Dakota Z. Smallridge, Kaitlyn E. Butts, Bijaya Bagale and Michael J. Tubergen

{"title":"The challenging conformer assignment of proline methyl ester from rotational spectroscopy†","authors":"Dinesh Marasinghe, Michael J. Carrillo, Dakota Z. Smallridge, Kaitlyn E. Butts, Bijaya Bagale and Michael J. Tubergen","doi":"10.1039/D5CP00898K","DOIUrl":"10.1039/D5CP00898K","url":null,"abstract":"The conformational structures of proline methyl ester (PrOMe) were modeled using CREST and further optimized using ωB97XD and MP2 methods with the 6-311++G(d,p) and aug-cc-pVDZ basis sets. Among the seven lowest energy conformers, two unique conformers, Cγ-exo/Cδ-endo and Cγ-endo, were found to be very close to the minimum energy. A rotational spectrum consisting of 51 rotational transitions was recorded for PrOMe using a cavity-based Fourier-transform microwave spectrometer in the range 9–20 GHz. The rotational transitions, split into resolved 14N-nuclear quadrupole hyperfine components for the A- and E-methyl-internal-rotation tunneling states, were fit using XIAM: A = 3678.4360(7) MHz, B = 1037.5616(3) MHz, and C = 944.2045(3) MHz, and the barrier to methyl torsion was found to be 393.54(9) cm−1. Comparison of model and spectroscopic moments of inertia is insufficient to conclusively assign the conformational structure. Analysis of second moments of inertia, dipole moment projections, and nuclear quadrupole hyperfine constants provides sufficient additional evidence to determine that the rotational spectrum is from a structure with an intramolecular hydrogen bond from the imino hydrogen to the carbonyl oxygen and with Cγendo.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 24","pages":" 13167-13173"},"PeriodicalIF":2.9,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cp/d5cp00898k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144211439","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