The Journal of Physical Chemistry A最新文献

Transition from Noncovalent Interaction to Covalent Bond Based on One-Electron Potential, Quantum Chemical Topology, and Molecular Face Theory. 基于单电子势、量子化学拓扑和分子面理论的从非共价相互作用到共价键的转变。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-06-30 DOI: 10.1021/acs.jpca.5c01773

Xin-Meng Liu, Dong-Xia Zhao, Zhong-Zhi Yang

{"title":"Transition from Noncovalent Interaction to Covalent Bond Based on One-Electron Potential, Quantum Chemical Topology, and Molecular Face Theory.","authors":"Xin-Meng Liu, Dong-Xia Zhao, Zhong-Zhi Yang","doi":"10.1021/acs.jpca.5c01773","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c01773","url":null,"abstract":"Noncovalent interactions and covalent bonds can be distinguished via quantum chemical topology analysis and molecular face theory, which are based on the potential acting on one electron in a molecule or molecular system (PAEM). A covalent bond forms when a PAEM bond critical point (BCP) occurs on the line connecting two atoms and when their molecular faces contact or fuse together, whereas a noncovalent interaction occurs between two adjacent atoms or chemical species when their molecular faces remain separate. The force acting on one electron within a molecule, which starts at infinity and ends at the BCP, forms nonoverlapping boundary surfaces that partition a molecule into distinct atomic regions. This is demonstrated with the following example reactions: H + H → H2, H + X → HX (X = F, Cl, Br, I), O (1D) + H2 → H2O, and S (1D) + H2 → H2S. The exploration of the physical quantities at PAEM critical points, such as the eigenvalues of the Hessian matrix, ellipticity, and electron interflow frequency, reveals their changing trends during the transition from a noncovalent interaction to a covalent bond or vice versa. These changes can help predict chemical bond formation or breakage, providing insight into chemical bonding.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144525518","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

Interactions of Neodymium(III) with Small-Molecule Ligands and Coronene Evaluated with DLPNO-CCSD(T). DLPNO-CCSD(T)评价钕（III）与小分子配体和冠烯的相互作用。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-06-30 DOI: 10.1021/acs.jpca.5c01797

Garima S Dobhal, Tiffany R Walsh

{"title":"Interactions of Neodymium(III) with Small-Molecule Ligands and Coronene Evaluated with DLPNO-CCSD(T).","authors":"Garima S Dobhal, Tiffany R Walsh","doi":"10.1021/acs.jpca.5c01797","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c01797","url":null,"abstract":"Determination of the interactions between critical metal ions and single-molecule ligands is key to improving sustainable reclamation processes for critical metals such as electrodeposition of these metals from liquid media. Neodymium, Nd, is one such critical metal that faces rising demand due to its application in permanent strong magnets used in wind turbines and in electric motors of electric vehicles. Previous experimental work identified that trace quantities of water facilitated Nd electrodeposition from ionic liquid (IL) media. Here, interactions of Nd3+ with TFSI- (bis(trifluoromethylsulfonyl)imide), a common anion in ILs, H2O (water), C2H6 (ethane, an approximation for long-chained phosphonium and ammonium cations in ILs) and coronene (an approximation for a graphitic electrode surface) are obtained using high-level DLPNO-CCSD(T) calculations. A range of binding orientations/conformations for each small molecule ligand are investigated. The nonadditivity effect is explored to identify the scaling of the interaction energy when one TFSI- is added to complexes of Nd(TFSI)x (where x = 1-3) and when one water molecule is added to a Nd(TFSI)3 complex. The most stable binding configuration is further analyzed using a relativistic Hamiltonian and also, using the local energy decomposition method. The LED method revealed that the interaction is mainly driven by electrostatics and polarization, and that correlation contributes insignificantly to the total interaction energy. This work provides high-quality benchmark data that cannot be obtained from experiment alone, to enable the design of high-quality force fields for simulation studies of the phenomena related to the electrodeposition processes.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144525515","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

Time Delay Distribution and Laser Stability in Arbitrary Detuning Asynchronous Optical Sampling. 任意失谐异步光采样中的延时分布和激光稳定性。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-06-30 DOI: 10.1021/acs.jpca.5c01853

L Antonucci, A Bonvalet, X Solinas, M Joffre

{"title":"Time Delay Distribution and Laser Stability in Arbitrary Detuning Asynchronous Optical Sampling.","authors":"L Antonucci, A Bonvalet, X Solinas, M Joffre","doi":"10.1021/acs.jpca.5c01853","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c01853","url":null,"abstract":"Arbitrary Detuning ASynchronous OPtical Sampling (ADASOPS) is an emerging technique for extending standard pump-probe experiments performed with two femtosecond lasers to multitimescale experiments, which are of great interest for the study of complex systems. Although no specific requirements are needed for laser repetition rates, their ratio determines the achievable delay distribution and therefore is strongly related to the temporal resolution of the technique. We report a detailed theoretical analysis of measurement performances with respect to laser repetition rates, and we validate our model with experimental data. In the case of amplified laser systems, we demonstrate that achieved delays are inherently correlated to the time interval between amplified pulses, which affects the pulse energy and can generate artifacts. Nevertheless, a deep understanding of the origin of such artifacts allows to suggest several compensation strategies, either during data analysis or at the conception of the experimental setup. Finally we present a new algorithm integrated into the ADASOPS device: by selecting pairs of probe pulses having the same elapsed time with respect to the previous pulse, it automatically compensates any effect of energy fluctuation.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144525517","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

Anion Resonances and Autodetachment Dynamics of Fluoranthene. 荧光蒽的阴离子共振和自脱离动力学。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-06-30 DOI: 10.1021/acs.jpca.5c03418

Kenneth D Wilson, Dillon C Dodge, Etienne Garand

引用次数: 0

High-Resolution Infrared Spectroscopy and Nuclear Spin Conversion of CH₃D in Solid Parahydrogen: Crystal Field Effects in Nuclear Spin Conversion. 固体对氢中CH3D的高分辨率红外光谱和核自旋转换：核自旋转换中的晶体场效应。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-06-30 DOI: 10.1021/acs.jpca.5c02100

Anh H M Nguyen, Ibrahim Muddasser, David T Anderson

{"title":"High-Resolution Infrared Spectroscopy and Nuclear Spin Conversion of CH3D in Solid Parahydrogen: Crystal Field Effects in Nuclear Spin Conversion.","authors":"Anh H M Nguyen, Ibrahim Muddasser, David T Anderson","doi":"10.1021/acs.jpca.5c02100","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02100","url":null,"abstract":"The nuclear spin conversion of CH3D isolated in solid parahydrogen (pH2) was investigated by high-resolution Fourier transform infrared (FTIR) spectroscopy. From the analysis of the temporal changes in the CH3D/pH2 rovibrational absorption spectra, the nuclear spin conversion rates associated with rotational relaxation from the J = 1, K = 1 state to the J = 0, K = 0 state were determined over the 1.5-4.3 K temperature range. As-deposited CH3D/pH2 samples contain two different crystal structures allowing the CH3D nuclear spin conversion rates to be measured for two different trapping sites, which revealed that CH3D trapped in hexagonal close-packed (hcp) crystal sites relax more than twice as fast as CH3D isolated in face centered cubic (fcc) crystal sites. The nuclear spin conversion rates of CH3D trapped in single substitution hcp crystal sites increase rapidly above 2.5 K, but the rates were almost temperature independent below 2 K leading to a limiting nonzero conversion rate of k = 2.76(8) × 10-3 min-1 at 1.58(1) K. Comparison of the temperature dependence of the CH3D nuclear spin conversion rate measured here with analogous measurements for CH4 and CD4 trapped in solid pH2 shows that CH3D relaxes with a rate constant intermediate between CH4 and CD4, and the faster relaxation for species containing deuterium atoms can be qualitatively explained by the quadrupole interaction that is absent in all hydrogen containing CH4 isotopomers.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144525514","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

Exploring the Mechanism of DABCO-Catalyzed Diastereoselective Cyclization for the Synthesis of Azetidine Nitrones. 探讨dabco催化非对映选择性环化合成氮杂环酮的机理。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-06-29 DOI: 10.1021/acs.jpca.5c02187

Rui-Ping Huo, Xiang Zhang, Kai-Xin Xie, Cai-Feng Zhang, Meng-Yao Li

引用次数: 0

Catalight─An Open-Source Automated Photocatalytic Reactor Package Illustrated through Plasmonic Acetylene Hydrogenation. Catalight──一个开源的自动光催化反应器套件，以等离子体乙炔加氢为例。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-06-29 DOI: 10.1021/acs.jpca.5c02883

B B Bourgeois, A X Dai, C C Carlin, L Yuan, A Al-Zubeidi, W H Cheng, D F Swearer, J A Dionne

{"title":"Catalight─An Open-Source Automated Photocatalytic Reactor Package Illustrated through Plasmonic Acetylene Hydrogenation.","authors":"B B Bourgeois, A X Dai, C C Carlin, L Yuan, A Al-Zubeidi, W H Cheng, D F Swearer, J A Dionne","doi":"10.1021/acs.jpca.5c02883","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02883","url":null,"abstract":"An open-source and modular Python package, Catalight, is developed and demonstrated to automate (photo)catalysis measurements. (Photo)catalysis experiments require studying several parameters to evaluate performance, including the temperature, gas flow rate and composition, illumination power, and spectral profile. Catalight orchestrates measurements over this complicated parameter space and systematically stores, analyzes, and visualizes the results. To showcase the capabilities of Catalight, we perform an automated apparent activation barrier measurement of acetylene hydrogenation over a plasmonic AuPd catalyst on an Al2O3 support, simultaneously varying laser power, wavelength, and temperature in a multiday experiment controlled by a simple Python script. Our chemical results unexpectedly show an increased activation barrier upon light excitation, contrary to previous findings for other plasmonic reactions and catalysts. We show that the reaction rate order with respect to both acetylene and hydrogen remains unchanged upon illumination, suggesting that molecular surface coverage is not changed by light. By analyzing the inhomogeneity of the laser-induced heating, we attribute these results to a partial photothermal effect combined with a photochemical/hot electron-driven mechanism. Our findings highlight the capabilities of a new experiment automation tool; explore the photocatalytic mechanism for an industrially relevant reaction; and identify systematic sources of error in canonical photocatalysis experimental procedures.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144525511","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

Multidimensional Morse/Long-Range Potential Energy Surface and Predicted Rotational Spectra of the CH₄-N₂ Complex. CH4-N2配合物的多维莫尔斯/远程势能面和预测旋转谱。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-06-29 DOI: 10.1021/acs.jpca.5c02139

Xiao-Long Zhang, Hui Li

引用次数: 0

Gradients of Ground and Excited States for CC2 and ADC(2) in Polarizable Continuum and Atomistic Embeddings within a Generalized PTED Coupling Scheme. 广义PTED耦合方案中CC2和ADC(2)的基态和激发态梯度及原子嵌入。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-06-29 DOI: 10.1021/acs.jpca.5c02873

Christof Hättig, Ansgar Pausch

{"title":"Gradients of Ground and Excited States for CC2 and ADC(2) in Polarizable Continuum and Atomistic Embeddings within a Generalized PTED Coupling Scheme.","authors":"Christof Hättig, Ansgar Pausch","doi":"10.1021/acs.jpca.5c02873","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02873","url":null,"abstract":"We present a state-specific implementation of ground and excitation energies and analytic gradients thereof for the approximate coupled-cluster singles and doubles model CC2 in polarizable environments that is suitable for the description of long-living charge-transfer excited states. It employs a reaction field potential equilibrated self-consistently with the target state density and includes linear response contributions to account for the excitonic coupling to the optical polarizability of the environment. The implementation is available in combination with the conductor-like screening model COSMO as a polarizable continuum model and an atomistic polarizable embedding in point multipoles and polarizabilities. For COSMO smooth potential energy surfaces and convergence of structure optimizations are obtained with a Gaussian charge model. For the algebraic-diagrammatic construction through second order, ADC(2), with COSMO, it is identical to an earlier implementation [Lunkenheimer, B. and Köhn, A. J. Chem. Theory Comput. 2013, 9, 977-994] but extends the latter to analytic gradients. Example applications are presented for structures, dipole moments, and emission energies of the charge-transfer and locally excited states of 4-(N,N-dimethylamino)benzonitrile and N-(9-anthryl)carbazole in different solvents. The results demonstrate that not only solvent shifts but also physically correct structures are obtained for strongly polar states in polarizable environments.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144525513","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

Structural Evolution of Boron Clusters upon Copper Doping in CuB_x^- (x = 4-6). cux - (x = 4-6)中铜掺杂后硼团簇的结构演化。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-06-27 DOI: 10.1021/acs.jpca.5c02881

Anton S Pozdeev, Hyun Wook Choi, Wei-Jia Chen, Lai-Sheng Wang, Ivan A Popov

{"title":"Structural Evolution of Boron Clusters upon Copper Doping in CuBx- (x = 4-6).","authors":"Anton S Pozdeev, Hyun Wook Choi, Wei-Jia Chen, Lai-Sheng Wang, Ivan A Popov","doi":"10.1021/acs.jpca.5c02881","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02881","url":null,"abstract":"Photoelectron spectroscopy and theoretical calculations are combined to elucidate the structures and chemical bonding of small boron clusters doped with a copper atom, CuBx- (x = 4-6). Relatively complex spectral features are observed and are interpreted by comparison with the theoretical results. Predicted global minimum structures of CuBx- (x = 4-6) evince that the Cu atom binds to an apex B atom in each cluster and does not significantly alter the planar boron framework of the corresponding Bx- clusters. Multielectronic transitions (shakeup processes) are observed in all three systems, a manifestation of strong electron correlation effects. Chemical bonding analyses show that the copper atom preferentially binds to the apex sites with the highest electron localization to form a Cu-B covalent bond. The structures and bonding of CuBx- (x = 4-6) are compared with those of the bare Bx- and the Cu2Bx- clusters, providing new insights into the structural and electronic evolution of Cu-doped boron clusters and the transition from Cu-B covalent bonding to ionic bonding.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504223","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