The Journal of Physical Chemistry A最新文献_第2页

Thermal CO₂ Adsorption and Activation on Copper Oxide Cluster Anions Cu_nO^- (n = 3-9). 铜氧化物簇阴离子CunO- (n = 3-9)对CO2的热吸附和活化。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-09 DOI: 10.1021/acs.jpca.5c05605

Rui-Ze Hui, Li-Jiao Zhang, Gao-Lei Hou, Sheng-Gui He, Ya-Ke Li

{"title":"Thermal CO2 Adsorption and Activation on Copper Oxide Cluster Anions CunO- (n = 3-9).","authors":"Rui-Ze Hui, Li-Jiao Zhang, Gao-Lei Hou, Sheng-Gui He, Ya-Ke Li","doi":"10.1021/acs.jpca.5c05605","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c05605","url":null,"abstract":"Understanding the active sites of copper (Cu)-based catalysts toward CO2 is a prerequisite for improving their rational design. The reactivity of copper oxide cluster anions CunO- (n = 3-9) and bare copper cluster anions Cun- toward CO2 has been investigated at room temperature by employing mass spectrometry combined with density functional theory (DFT) calculations. Only adsorption products are observed for the reaction of CunO- with CO2. There is almost no observation for the reaction between bare Cun- and CO2 under our reaction conditions, and only a tiny adsorption of CO2 on Cu5- cluster anions was observed. Our experimental results indicate that the doping of an O atom into bare copper cluster anions can boost the CO2 adsorption capability at room temperature. Theoretical analysis indicates that the introduction of the O atom could change the charge distribution on bare copper cluster anions, making Lewis acid-base pairs Cu-O and Cuδ+-Cuδ-, which promotes the CO2 adsorption with the formation of the O-C (Cu-C) and Cu-O bonds. The reaction rate constants exhibit size dependence yet remain on the same order of magnitude (∼10-11 cm3·s-1). More specifically, the reaction rates generally increase with larger cluster size. However, the n = 8 cluster exhibits a markedly lower reaction rate compared to both the n = 7 and n = 9 clusters, which could stem from its thermodynamically and kinetically less favorable reaction pathway. Our work provides molecular-level insights into the CO2 adsorption and activation on anoxic copper catalyst surface by using mass spectrometry and DFT calculations.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028524","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Quantum Information Theory on Sparse Wave Functions and Applications for Quantum Chemistry. 稀疏波函数的量子信息理论及其在量子化学中的应用。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-09 DOI: 10.1021/acs.jpca.5c02137

Davide Materia, Leonardo Ratini, Leonardo Guidoni

{"title":"Quantum Information Theory on Sparse Wave Functions and Applications for Quantum Chemistry.","authors":"Davide Materia, Leonardo Ratini, Leonardo Guidoni","doi":"10.1021/acs.jpca.5c02137","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02137","url":null,"abstract":"In recent years Quantum Computing prominently entered in the field of Computational Chemistry, importing and transforming computational methods and ideas originally developed within other disciplines, such as Physics, Mathematics and Computer Science into algorithms able to estimate quantum properties of atoms and molecules on present and future quantum devices. An important role in this contamination process is attributed to Quantum Information techniques, having the 2-fold role of contributing to the analysis of electron correlation and entanglements and guiding the construction of wave function variational ansatzes for the Variational Quantum Eigensolver technique. This paper introduces the tool SparQ (Sparse Quantum state analysis), designed to efficiently compute fundamental quantum information theory observables on post-Hartree-Fock wave functions sparse in their definition space. The core methodology involves mapping Fermionic wave functions to qubit space using Fermionic-to-qubits transformations and leveraging the sparse nature of these wave functions to evaluate observables and properties of the wave function. The effectiveness of SparQ is validated by analyzing the mutual information matrices of wave functions for the water molecule and the entropy of ∼102 qubits describing the benzene molecule. This highlights its capability to handle large-scale quantum systems, limited mainly by the capabilities of quantum chemical methods used to retrieve the wave functions. The results indicate that quantum information theoretical analysis, so far limited to traditional tensor network methods and study of transition operators, can be applied to all post-Hartree-Fock wave functions, extending their applications to larger and more complex chemical systems.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Spectroscopy and Theory of Acetylene Coupling Reactions in Ti⁺(C₂H₂)_n Complexes. Ti+(C2H2)n配合物中乙炔偶联反应的光谱与理论。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-09 DOI: 10.1021/acs.jpca.5c05395

Anna G Poncelet, John R C Blais, Richard B Odonkor, Michael A Duncan

{"title":"Spectroscopy and Theory of Acetylene Coupling Reactions in Ti+(C2H2)n Complexes.","authors":"Anna G Poncelet, John R C Blais, Richard B Odonkor, Michael A Duncan","doi":"10.1021/acs.jpca.5c05395","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c05395","url":null,"abstract":"Ti+(C2H2)n complexes produced by laser vaporization in a supersonic expansion are investigated with mass spectrometry, infrared laser photodissociation spectroscopy, and UV laser photodissociation. The mass distributions of the cluster ions produced are found to vary significantly with the sample rod mounting configuration in the source. For infrared spectroscopy experiments, the so-called \"offset\" rod mounting produces colder conditions than the \"cutaway\" configuration, which allows tagging the ions with one or more argon atoms for the n = 1 and 2 complexes. Infrared photodissociation spectra for these ions allow the identification of cation-π complexes (n = 1, 2) and reaction products from acetylene coupling (n = 2). A TiC4 metallacycle ion is identified by experiment and theory as the dominant reaction product. Larger complexes could not be tagged with argon under our conditions and therefore infrared spectra could not be measured. Under warmer expansion conditions with the cutaway rod configuration, prominent Ti+(C2H2)3 and Ti+(C2H2)6 ions are formed. UV photodissociation patterns for these ions are found to be almost identical to those for the corresponding Ti+(C6H6) and Ti+(C6H6)2 ions, suggesting that acetylene cyclization reactions have produced benzene and di-benzene complexes. Reaction path computations for both the n = 2 and 3 complexes investigate the energetics of the cyclization reactions in these systems.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028598","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Designing Spin-Correlated Radical Ion Pairs for Quantum Sensing of Electric Fields: Effect of Electron-Nuclear Hyperfine Coupling. 设计用于电场量子传感的自旋相关自由基离子对：电子-核超精细耦合的影响。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-08 DOI: 10.1021/acs.jpca.5c03803

Fangbai Xie, Angelo Carella, Ryan M Young, Marilena Di Valentin, Matthew D Krzyaniak, Michael R Wasielewski

{"title":"Designing Spin-Correlated Radical Ion Pairs for Quantum Sensing of Electric Fields: Effect of Electron-Nuclear Hyperfine Coupling.","authors":"Fangbai Xie, Angelo Carella, Ryan M Young, Marilena Di Valentin, Matthew D Krzyaniak, Michael R Wasielewski","doi":"10.1021/acs.jpca.5c03803","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03803","url":null,"abstract":"Light-driven formation of radical ion pairs that occurs much faster than their electron spin dynamics results in correlated spins whose coherence properties can be used as a quantum-based electric field sensor. This results from the radical ion pair having charge and spin distributions that track one another. Thus, electric field induced changes in the distance between the two charges are reflected in the spin-spin distance that can be measured directly using out-of-phase electron spin echo envelope modulation (OOP-ESEEM), a pulse-EPR technique. OOP-ESEEM produces oscillations whose frequency depends on the spin-spin exchange (J) and dipolar (D) interactions as well as the electron-nuclear hyperfine couplings of the radicals. To date, analyses of OOP-ESEEM data have focused predominately on determination of J and D, largely because D serves to measure the spin-spin distance. In this study we compare the OOP-ESEEM signals obtained from radical ion pairs that are fully deuterated with those that contain hydrogen. The results show that low modulation amplitudes occur in the OOP-ESEEM data using deuterated radicals, making it difficult to accurately measure radical ion pair distances. Further, the use of hydrogen-containing radicals provides the modulation amplitude enhancement necessary to measure small distances accurately using OOP-ESEEM data despite the somewhat shorter electron spin coherence times of the hydrogen-containing radical ion pairs. This is an important consideration when designing photogenerated radical ion pairs to serve as quantum sensors of electric fields.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145022433","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Conformation of Gas-Phase Crown Ether Complexes with Alkaline-Earth and Transition Metal Ions Studied by Cryogenic Ion Mobility-Mass Spectrometry. 低温离子迁移-质谱法研究碱-土和过渡金属离子气相冠醚配合物的构象。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-08 DOI: 10.1021/acs.jpca.5c04497

Ryosuke Ito, Keijiro Ohshimo, Fuminori Misaizu

{"title":"Conformation of Gas-Phase Crown Ether Complexes with Alkaline-Earth and Transition Metal Ions Studied by Cryogenic Ion Mobility-Mass Spectrometry.","authors":"Ryosuke Ito, Keijiro Ohshimo, Fuminori Misaizu","doi":"10.1021/acs.jpca.5c04497","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c04497","url":null,"abstract":"The gas-phase structures of dibenzo-24-crown-8 (DB24C8) and dinaphtho-24-crown-8 (DN24C8) complexes with divalent metal ions (Mg2+, Ca2+, Sr2+, Ba2+, Fe2+, Ni2+, and Zn2+) were investigated by cryogenic ion mobility-mass spectrometry (IM-MS) in combination with density functional theory calculations. Several complexes, particularly those of DN24C8, exhibited multiple coexisting conformers. DFT-optimized structures were classified based on the relative orientation of the two aromatic rings in the crown ether. For most metal ions, closed conformers, with the aromatic rings closely stacked, were stabilized in the DN24C8 complexes by enhanced π-π interactions, whereas closed' conformers, with the aromatic rings laterally displaced, were favored in the DB24C8 complexes due to intramolecular electrostatic repulsion. In contrast, open conformers, with the aromatic rings widely separated, were strongly preferred in the Ni2+ complexes, which was attributed to mer/fac isomerism in the octahedral coordination. These results highlight the important roles of ion size, charge, and coordination geometry in determining the conformational preferences of crown ether complexes in the gas phase, providing molecular-level insight into ion selectivity.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145013500","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Bond Dissociation Energies of RuC, RhC, OsC, IrC, and PtC Measured by Resonant Three-Photon Ionization Spectroscopy. 用共振三光子电离光谱测量RuC、RhC、OsC、IrC和PtC的键解离能。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-08 DOI: 10.1021/acs.jpca.5c04466

Kimberly H Tomchak, Michael D Morse

{"title":"Bond Dissociation Energies of RuC, RhC, OsC, IrC, and PtC Measured by Resonant Three-Photon Ionization Spectroscopy.","authors":"Kimberly H Tomchak, Michael D Morse","doi":"10.1021/acs.jpca.5c04466","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c04466","url":null,"abstract":"Resonant three-photon ionization spectroscopy has been used to study the late 4d and 5d transition metal carbides RuC, RhC, OsC, IrC, and PtC. These species, like most diatomic transition metals with open nd subshells, exhibit an exceptionally high density of states near the ground separated atom limit. Spin-orbit and nonadiabatic interactions provide a means for the molecules to rapidly dissociate as soon as the bond dissociation energy (BDE) is exceeded. The result is a sharp predissociation threshold that is identified as the BDE. The high BDEs of these five molecules required the use of two tunable lasers to reach the BDE. Measured values of D0(RuC) = 6.312(2) eV, D0(RhC) = 6.007(2) eV, D0(OsC) = 6.427(2) eV, D0(IrC) = 6.404(2) eV, and D0(PtC) = 6.260(2) eV were obtained, where the value is parentheses represents the estimated error limit in units of the last quoted digit. A new electronic state of PtC, tentatively assigned as the c3Σ1+ state, has been found with T0 = 22,442 cm-1. These BDEs are combined with recently measured ionization energies to obtain BDEs of the associated cations. Electronic structure calculations are also reported to investigate the chemical bonding in more detail. Trends in the BDEs of the diatomic transition metal carbides are also discussed.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145013532","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 Subsystem Perspective on Vibrational Coupled Cluster Response Theory. 振动耦合簇响应理论的子系统视角。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-08 DOI: 10.1021/acs.jpca.5c03752

Lars Henrik Olsen, Carolin König, Ove Christiansen

{"title":"A Subsystem Perspective on Vibrational Coupled Cluster Response Theory.","authors":"Lars Henrik Olsen, Carolin König, Ove Christiansen","doi":"10.1021/acs.jpca.5c03752","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03752","url":null,"abstract":"Based on a theoretical analysis of systems composed of subsystems described using a coupled cluster parametrization, we developed a vibrational coupled cluster embedding theory specifically tailored for the computation of response properties. This work identifies several strategies for calculating excitation energies, transition probabilities, and other response functions in large systems of interacting subsystems. A particularly effective embedding approach was formulated around a Lagrangian with multilinear interaction terms, yielding a structure that is nonlinear in both coupled cluster amplitudes and multipliers. Within this framework, we derived the corresponding response functions and associated eigenvalue equations. We also explored partitioning strategies for these equations, resulting in approximate exciton-like models that combine computational efficiency with conceptual clarity. This exciton-inspired methodology establishes a unified framework for computing excitation energies and transition properties in both electronic and vibrational coupled cluster response theories, applicable in both vacuum and embedded contexts. It provides a theoretical foundation for the future development of efficient methods for simulating vibrational spectra in extended systems.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145013535","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

How Isomer and Conformer Structures Impact Dissociation Dynamics of Alkane Radical Cations. 异构体和构象结构如何影响烷烃自由基阳离子的离解动力学。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-07 DOI: 10.1021/acs.jpca.5c04290

Madison K Minvielle, Mikaela Aftel, Timothy Hill, Hugo A López Peña, Katharine Moore Tibbetts

{"title":"How Isomer and Conformer Structures Impact Dissociation Dynamics of Alkane Radical Cations.","authors":"Madison K Minvielle, Mikaela Aftel, Timothy Hill, Hugo A López Peña, Katharine Moore Tibbetts","doi":"10.1021/acs.jpca.5c04290","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c04290","url":null,"abstract":"Ionization of alkanes to form radical cations activates their otherwise unreactive C-H bonds, facilitating important chemical processes such as hydrocarbon cracking. This work investigates the radical cation dissociation dynamics of hexane (C6H14) structural isomers by using femtosecond time-resolved mass spectrometry and quantum chemical calculations. All five isomers exhibit competition between the yields of fragment ions arising from direct C-C bond cleavage or dissociative rearrangement with hydrogen migration on dynamical time scales of ∼50-300 fs, suggesting that hydrogen migration in the metastable cations operates on such short time scales. Additional isomer- and conformer-specific dynamics are observed. Preferential dissociation pathways in the branched isomers are found to arise from geometric relaxation to cation structures with one elongated C-C bond. Coherent vibrational excitation along this elongated C-C bond in 3-methylpentane and 2,3-dimethylbutane results in ion yield oscillations in the first ∼300-400 fs after ionization. Enhanced depletion of the molecular ion signal in n-hexane compared to that in the branched isomers is attributed to a strongly coupled excited state in the most populated conformer that can be accessed by a two-photon transition. Collectively, these results provide a foundational understanding of dissociation dynamics in alkane radical cations and how these dynamics are affected by specific isomer and conformer structures.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145013522","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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 and Kinetic Insights into Nitrogen Chemistry: NH₂-Mediated H-Abstraction and HCN Addition Pathways in NH₃/Ethanol Combustion. 氮化学的机理和动力学见解：NH3/乙醇燃烧中nh2介导的h萃取和HCN加成途径。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-06 DOI: 10.1021/acs.jpca.5c03451

Tong Yan, Pan Wang, Jianmin Liu, Jinsheng Zhang, Lidong Zhang

{"title":"Mechanistic and Kinetic Insights into Nitrogen Chemistry: NH2-Mediated H-Abstraction and HCN Addition Pathways in NH3/Ethanol Combustion.","authors":"Tong Yan, Pan Wang, Jianmin Liu, Jinsheng Zhang, Lidong Zhang","doi":"10.1021/acs.jpca.5c03451","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03451","url":null,"abstract":"To elucidate possible mechanisms of nitrogen chemistry between ammonia (NH3) and ethanol, the potential pathways of ethanol radicals (Wa, Wb, and Wc) following H-abstraction by NH2 radicals were primarily investigated including HCN addition, H-transfer, and dissociation reactions by quantum chemical calculations. The rate constants were solved in the master equation based on RRKM and TST theory and fitted to the Arrhenius equation. The results demonstrate that H-abstraction from C2H5OH by NH2 at the b-site is the most competitive, facilitating subsequent HCN addition. The HCN addition-entranced channel exhibits a negative temperature coefficient (NTC) behavior at 0.01 atm, and the onset of this effect is progressively delayed with pressure. The low-temperature reaction path of ethanol radicals with HCN is dominated by the initial adduct (WaHCN, WbHCN, and WcHCN) formation and subsequent isomerization. The multiple dissociation product channels become more competitive with temperature, especially the HCNH elimination. Findings from this study identify new growth pathways for NPAHs and OPAHs in the reaction of straight-chain molecules with HCN and provide comprehensive kinetic insights.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145008039","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Barrier-Free Zinc Dimer Rotor on a Borozene-like BSi₅^3- Stator: The Smallest Molecular Compass with Planar Pentacoordinate Boron. 硼类BSi53定子上的无障碍锌二聚体转子：平面五坐标硼的最小分子罗盘。

IF 2.8 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-09-06 DOI: 10.1021/acs.jpca.5c04721

Bo Jin, Miao Yan, Lin-Yan Feng, Zai-Ran Wang, Chang-Qing Miao, Ying-Jin Wang

{"title":"Barrier-Free Zinc Dimer Rotor on a Borozene-like BSi53- Stator: The Smallest Molecular Compass with Planar Pentacoordinate Boron.","authors":"Bo Jin, Miao Yan, Lin-Yan Feng, Zai-Ran Wang, Chang-Qing Miao, Ying-Jin Wang","doi":"10.1021/acs.jpca.5c04721","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c04721","url":null,"abstract":"This work introduces the novel anionic cluster BSi5Zn2- as the smallest molecular \"compass\", featuring a unique two-layered architecture with a planar pentacoordinate boron (ppB) center. The cluster comprises a quasi-planar BSi53- stator─a silicon-based analogue of borozene with σ/π double aromaticity (6π + 10σ delocalized electrons)─and a Zn2 rotor dimer. High-level calculations (CCSD(T)//PBE0-D3) reveal an ultralow rotational barrier of 0.02 kcal mol-1 for the Zn2 dimer, enabling barrier-free 360° rotation on the stator surface, as confirmed by Born-Oppenheimer molecular dynamics (BOMD) simulations at 298-800 K. Bonding analysis attributes this exceptional fluxionality to a hybrid ionic-covalent interaction best described as [Zn2+][BSi52-], where charge transfer (Zn2 → BSi5) ensures electrostatic stability, while the delocalized electron cloud of the aromatic stator minimizes rotational resistance. This design successfully extends to BGe5Zn2- but fails for BSn5Zn2- due to size mismatch, highlighting the synergy of electronic delocalization and geometric constraints. The study pioneers the extension of nanorotor design from pure boron clusters to group 14 element-based platforms with benzene-like σ/π delocalization, establishing the smallest molecular compass based on a minimal stator (6-atom BSi53-) and establishing a new paradigm for dynamic molecular machines.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145005646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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