The Journal of Physical Chemistry A最新文献_第4页

Revealing Structural Transformations of Ligand Detachment in Cu Clusters: Insights from Ion Mobility Spectrometry. 揭示铜簇中配体脱离的结构转变：来自离子迁移谱法的见解。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-22 DOI: 10.1021/acs.jpca.5c01354

Lili Zhang, Ruixian Guo, Cong Fang, Detong Kong, Dingding Lv, Xiaoyan Sun

{"title":"Revealing Structural Transformations of Ligand Detachment in Cu Clusters: Insights from Ion Mobility Spectrometry.","authors":"Lili Zhang, Ruixian Guo, Cong Fang, Detong Kong, Dingding Lv, Xiaoyan Sun","doi":"10.1021/acs.jpca.5c01354","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c01354","url":null,"abstract":"Ligands play a pivotal role in stabilizing clusters and tuning their properties. However, during the exploration of the cluster's intrinsic properties, ligands often experience partial detachment, which imparts unique characteristics and enhances their functional flexibility. While previous studies have largely focused on macroscopic changes in composition and size, the atomic-level structural evolution of clusters upon ligand loss remains insufficiently explored, with direct experimental evidence being scarce. In this study, by utilizing Cu6HL6 and its fragment Cu4L4 (L = 2-mercaptobenzimidazole) clusters as pertinent model systems, we systematically investigated the structure transformation of the stepwise removal of one and two ligands, leveraging collision induced dissociation (CID) with traveling wave ion mobility-mass spectrometry (TWIM-MS) as a powerful analytical approach. Based on a detailed analysis of the collision cross-section combined with ab initio molecular dynamics (AIMD), it was found that the detachment of a single ligand can lead to a significant distortion of the Cu6 core structure. Further ligand loss subsequently induced a reorganization of the Cu6 core, resulting in a reshaped configuration. Moreover, for a smaller Cu4L4 cluster, it also experienced distortion upon the loss of a single ligand. Interestingly, this process resulted in the formation of two distinct Cu4L3 isomers, which could be attributed to the repulsion between the ligands of charged Cu4L3 in the gas phase. While it was generally assumed that ligand removal has little impact on the nanocluster structure, our results offer new atomic-level insights into the structural dynamics associated with ligand detachment.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144126225","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

Influence on the Optical and Electronic Properties of Graphene Quantum Dots Originating from the S-Doping Site: A Theoretical Investigation. s掺杂对石墨烯量子点光学和电子特性影响的理论研究。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-22 Epub Date: 2025-05-10 DOI: 10.1021/acs.jpca.5c00370

Fengjiao Zhao, Tianfu Zhang, Shuxin Sui, Zhen Chen

{"title":"Influence on the Optical and Electronic Properties of Graphene Quantum Dots Originating from the S-Doping Site: A Theoretical Investigation.","authors":"Fengjiao Zhao, Tianfu Zhang, Shuxin Sui, Zhen Chen","doi":"10.1021/acs.jpca.5c00370","DOIUrl":"10.1021/acs.jpca.5c00370","url":null,"abstract":"The optical and electronic properties of sulfur-doped graphene quantum dots (GQDs) have been theoretically investigated using DFT/TD-DFT methods in water (B3LYP/6-31G/SMD). Both edge and core sites for doping have been considered. Simulation results reveal that edge-doped sulfydryl (-SH) presents no significant influence on the energy level distribution compring with the pristine GQDs which results in idential absorption spectra, however, the nonzero oscillator strength (f) of S0-S1 transition of edge-doped S-GQDs enables fluorescence emission (@∼450 nm) whereas the GQDs yield no fluorescence emission based on Kasha's rule. Moreover, the S doping of GQDs at the core sites dramatically raises the HOMO energy level and regulates the electron transfer process and the corresponding density of states during electron transition. This eventually decreases the HOMO-LUMO gaps, enabling strong fluorescence emission in the near-infrared region, which suggests that the S-GQDs at the skeleton sites have great potential for application in the bioimaging field.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4357-4363"},"PeriodicalIF":2.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951308","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

Ground and First Excited States of the NaSr Molecule: Experimental and Theoretical Study. NaSr分子的基态和第一激发态：实验和理论研究。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-22 Epub Date: 2025-05-08 DOI: 10.1021/acs.jpca.5c01878

Jacek Szczepkowski, Marcin Gronowski, Matylda Olko, Romain Vexiau, Michał Tomza, Olivier Dulieu, Paweł Kowalczyk, Włodzimierz Jastrzebski

引用次数: 0

1,6-Diazapyrene: A Novel, Well-Defined, Small-Size Prototype System for Nitrogen-Containing PAHs. 1,6-二氮芘：一种新的，定义良好的，小尺寸的含氮多环芳烃原型系统。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-22 Epub Date: 2025-05-12 DOI: 10.1021/acs.jpca.5c01474

Indranil Bhattacharjee, Liangxuan Wang, Nerea Gonzalez-Sanchis, Begoña Milián-Medina, Rafael Ballesteros, Reinhold Wannemacher, Rafael Ballesteros-Garrido, Johannes Gierschner

引用次数: 0

Clarifying the Identity of the m/z 36 Ion in Water Microdroplet Mass Spectra. 澄清水微滴质谱中m/ z36离子的同一性。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-22 Epub Date: 2025-05-13 DOI: 10.1021/acs.jpca.5c02557

Xiaowei Song, Lecheng Lyu, Jinheng Xu, Dong Xing, Xinxing Zhang, Richard N Zare

引用次数: 0

Effect of Hydrogen Bonding on Ultrafast Intersystem Crossing in 7-Diethylaminothiocoumarin. 氢键对7-二乙基氨基硫代香豆素超快速体系间交叉的影响。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-22 Epub Date: 2025-05-13 DOI: 10.1021/acs.jpca.5c00901

Abhijit Dutta, Suman Bhowmik, Sujit Kumar Ghosh, Vaidhyanathan Ramamurthy, Pratik Sen

{"title":"Effect of Hydrogen Bonding on Ultrafast Intersystem Crossing in 7-Diethylaminothiocoumarin.","authors":"Abhijit Dutta, Suman Bhowmik, Sujit Kumar Ghosh, Vaidhyanathan Ramamurthy, Pratik Sen","doi":"10.1021/acs.jpca.5c00901","DOIUrl":"10.1021/acs.jpca.5c00901","url":null,"abstract":"Thiocarbonyls exhibit unique photophysical properties, characterized by rapid intersystem crossing (ISC) due to favorable singlet-triplet energetics and enhanced spin-orbit coupling. However, the role of hydrogen bonding in modulating the ISC remains underexplored. This study investigates the effect of solvent-solute hydrogen bonding on the ISC dynamics of 7-(diethylamino)-4-methyl-2-sulfanylidene-2H-chromen-2-one (thiocoumarin 1, TC1) using steady-state and time-resolved spectroscopy, complemented by theoretical calculations. Experimental data reveal that in methanol, hydrogen bonding leads to increased fluorescence quantum yield, prolonged singlet-state lifetime, and reduced triplet yield compared to aprotic acetonitrile. Time-resolved spectroscopy identifies an additional long-lived emissive singlet state in methanol, attributed to a hydrogen-bonded state, which slows ISC. Theoretical calculations demonstrate that hydrogen bonding alters the electronic structure and constrains ISC along key nuclear coordinates, including the C═S bond vibration and dihedral angles, leading to decreased triplet formation. These findings provide mechanistic insights into hydrogen-bonding-mediated control of ISC in thiocoumarins, with implications for designing functional materials with tunable photophysical properties.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4414-4425"},"PeriodicalIF":2.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143955964","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

Deciphering the Structural and Electronic Properties of RuSi₃^-/0 Clusters: Insights from Anion Photoelectron Spectroscopy and Theoretical Analysis. 破译RuSi3-/0簇的结构和电子性质：来自阴离子光电子能谱和理论分析的见解。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-22 Epub Date: 2025-05-09 DOI: 10.1021/acs.jpca.5c01905

Sheng-Jie Lu, Zhong-Xin Sun

{"title":"Deciphering the Structural and Electronic Properties of RuSi3-/0 Clusters: Insights from Anion Photoelectron Spectroscopy and Theoretical Analysis.","authors":"Sheng-Jie Lu, Zhong-Xin Sun","doi":"10.1021/acs.jpca.5c01905","DOIUrl":"10.1021/acs.jpca.5c01905","url":null,"abstract":"Transition metal (TM) silicides have attracted significant attention in materials science due to their desirable physical properties and varied applications across industries ranging from microelectronics to catalysis. This study uniquely explores the structural and bonding characteristics of ruthenium-doped silicon clusters, specifically RuSi3, presenting new experimental and computational insights into these anionic and neutral species. Mass-selected photoelectron spectroscopy, alongside advanced theoretical techniques including density functional theory (DFT) and high-precision coupled cluster (CCSD(T)) methods, was employed to probe the electronic structures and energetic properties of RuSi3- anion and its neutral counterpart. The results reveal the presence of multiple isomers within RuSi3-, characterized by distinct electronic configurations, and show a strong correlation between experimental and theoretical vertical detachment energy (VDE). Notably, the findings indicate that the covalent interactions and charge distributions in these clusters significantly influence their stability and reactivity.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4505-4512"},"PeriodicalIF":2.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951611","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 Phase-Space Electronic Hamiltonian for Molecules in a Static Magnetic Field II: Quantum Chemistry Calculations with Gauge Invariant Atomic Orbitals. 静态磁场中分子的相空间电子哈密顿量II：规范不变原子轨道的量子化学计算。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-22 Epub Date: 2025-05-12 DOI: 10.1021/acs.jpca.4c07905

Mansi Bhati, Zhen Tao, Xuezhi Bian, Jonathan Rawlinson, Robert Littlejohn, Joseph E Subotnik

{"title":"A Phase-Space Electronic Hamiltonian for Molecules in a Static Magnetic Field II: Quantum Chemistry Calculations with Gauge Invariant Atomic Orbitals.","authors":"Mansi Bhati, Zhen Tao, Xuezhi Bian, Jonathan Rawlinson, Robert Littlejohn, Joseph E Subotnik","doi":"10.1021/acs.jpca.4c07905","DOIUrl":"10.1021/acs.jpca.4c07905","url":null,"abstract":"In a companion paper, we have developed a phase-space electronic structure theory of molecules in magnetic fields, whereby the electronic energy levels arise from diagonalizing a phase-space Hamiltonian ĤPS(X, P, G, B) that depends parametrically on nuclear position and momentum. The resulting eigenvalues are translationally invariant; moreover, if the magnetic field is in the z-direction, then the eigenvalues are also invariant to rotations around the z-direction. However, like all Hamiltonians in a magnetic field, the theory has a gauge degree of freedom (corresponding to the position of the magnetic origin in the vector potential), and requires either (i) formally, a complete set of electronic states or (ii) in practice, gauge-invariant atomic orbitals (GIAOs) in order to realize such translational and rotational invariance. Here we describe how to implement a phase-space electronic Hamiltonian using GIAOs within a practical electronic structure package (in our case, Q-Chem). We further show that novel phenomena can be observed with finite B-fields, including minimum energy structures with Πmin ≠ 0, indicating nonzero electronic motion in the ground-state.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4573-4590"},"PeriodicalIF":2.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143952467","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

Rapid Discovery of Graphene Nanoflakes with Desired Absorption Spectra Using DFT and Bayesian Optimization with Neural Network Kernel. 利用DFT和神经网络核贝叶斯优化快速发现具有理想吸收光谱的石墨烯纳米片。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-22 Epub Date: 2025-05-08 DOI: 10.1021/acs.jpca.5c00405

Şener Özönder, Hatice Kübra Küçükkartal

{"title":"Rapid Discovery of Graphene Nanoflakes with Desired Absorption Spectra Using DFT and Bayesian Optimization with Neural Network Kernel.","authors":"Şener Özönder, Hatice Kübra Küçükkartal","doi":"10.1021/acs.jpca.5c00405","DOIUrl":"10.1021/acs.jpca.5c00405","url":null,"abstract":"Grid searching a large and high-dimensional chemical space with density functional theory (DFT) to discover new materials with desired properties is prohibitive due to the high computational cost. We propose an approach utilizing Bayesian optimization (BO) with an artificial neural network kernel to enable an efficient and low-cost guided search on the chemical space, avoiding costly brute-force grid search. This method leverages the BO algorithm, where the kernel neural network trained on a limited number of DFT results determines the most promising regions of the chemical space to explore in subsequent iterations. This approach aims to discover new materials with target properties while minimizing the number of DFT calculations required. To demonstrate the effectiveness of this method, we investigated 63 doped graphene quantum dots (GQDs) with sizes ranging from 1 to 2 nm to find the structure with the highest light absorption. Using time-dependent DFT (TDDFT) only 12 times, we achieved a significant reduction in computational cost, approximately 20% of what would be required for a full grid search. Considering that TDDFT calculations for a single GQD require about half a day of wall time on high-performance computing nodes, this reduction is substantial. Our approach can be generalized to the discovery of new drugs, chemicals, crystals, and alloys in high-dimensional and large chemical spaces, offering a scalable solution enabled by the neural network kernel.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4591-4600"},"PeriodicalIF":2.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143952825","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

Room Temperature Gas-Phase Detection and Formation Gibbs Energy of the Water Dimethyl Ether Bimolecular Complex. 水二甲醚双分子配合物的室温气相检测和形成吉布斯能。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-22 Epub Date: 2025-05-07 DOI: 10.1021/acs.jpca.5c01130

Alexander Kjaersgaard, Dhritabrata Pal, Emil Vogt, Tine Elmelund Skovbo, Henrik G Kjaergaard

{"title":"Room Temperature Gas-Phase Detection and Formation Gibbs Energy of the Water Dimethyl Ether Bimolecular Complex.","authors":"Alexander Kjaersgaard, Dhritabrata Pal, Emil Vogt, Tine Elmelund Skovbo, Henrik G Kjaergaard","doi":"10.1021/acs.jpca.5c01130","DOIUrl":"10.1021/acs.jpca.5c01130","url":null,"abstract":"Hydrated complexes are of general interest for understanding nucleation processes in the atmosphere, where water is abundant, especially as the role of whether water enhances or inhibits nucleation is still uncertain. We have recorded the Fourier transform infrared absorption spectrum of the water dimethyl ether bimolecular complex in the gas phase at room temperature. Four distinct bands are observed and assigned. The equilibrium constant of complex formation is determined from the experimental integrated absorbance of the bands and the corresponding calculated intensities. The calculated band intensities are obtained with a 9D reduced-dimensional variational local mode model with the CCSD(T)-F12a/cc-pVDZ-F12 potential energy and dipole moment surfaces. A similar equilibrium constant for a majority of the observed bands is obtained, with an average value of 0.042 ± 0.003 at T = 298 K. The water dimethyl ether complex studied here is similar to the water dimer, and our determined equilibrium constant may serve as a reasonable estimate for that of water dimer, which is especially relevant in atmospheric chemistry.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4438-4446"},"PeriodicalIF":2.7,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143952827","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