The Journal of Physical Chemistry A最新文献

{"title":"Luminescence Study of DPAC-PCN Doped in Isomeric Host Materials.","authors":"Xiaofei Wang, Zhimin Wu, Ying Cao, Jiaxin Zhou, Yuzhi Song, Jianzhong Fan, Lili Lin, Jing Li","doi":"10.1021/acs.jpca.5c06281","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c06281","url":null,"abstract":"<p><p>The rational design of thermally activated delayed fluorescence (TADF) emitters and their associated host materials has become a critical research frontier in organic light-emitting diode (OLED) technology. In this work, the influence of isomeric host materials on the luminescent properties of donor-acceptor (D-A)-type TADF emitter DPAC-PCN is investigated. Molecular dynamics simulation was performed to obtain the morphological structures of doped films, and the quantum mechanics/molecular mechanics (QM/MM) method was employed to calculate the excited state properties. The results demonstrate that host 3CzAcPy leads to a larger energy gap and a shorter emission wavelength of DPAC-PCN compared to its isomeric 9CzAcPy. In the DPAN-PCN:3CzAcPy-doped film, different residues show various luminescent properties, which may affect the luminescence purity of the OLEDs. In contrast, the luminescence of residues in the DPAN-PCN:9CzAcPy-doped film is similar to each other. This study indicates that the luminescence properties of DPAC-PCN are highly sensitive to the host material and provide a theoretical foundation for selecting an optimal host material for DPAC-PCN.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145336041","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}

{"title":"Tuning Lanthanide Binding with Phenanthroline-Based Diamides via Electron-Donating and Electron-Withdrawing Groups.","authors":"Anton S Pozdeev, Alexander S Ivanov, Santa Jansone-Popova, De-En Jiang","doi":"10.1021/acs.jpca.5c03506","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03506","url":null,"abstract":"<p><p>Efficient separation of lanthanides is challenging due to their similar sizes and properties but continues to attract intensive theoretical and experimental interest. 1,10-phenanthroline-2,9-diamide (DAPhen) ligands are promising in solvent extraction separations of f-elements due to their combinations of soft N and hard O donors, but how the conjugated electrons and charge densities on the N and O donors can be further manipulated to tune the binding with lanthanides has not been fully explored. By substituting hydrogen atoms on the phenanthroline (Phen) skeleton with various electron-donating and electron-withdrawing groups, here we assess their impact on the complexation properties crucial for lanthanide separation. Employing advanced quantum chemical techniques, we have found that these substitutions significantly affect binding energies, although they have a relatively weak influence on selectivity for the whole lanthanide series. By elucidating the bonding nature in the studied lanthanide complexes, we provide a unified interpretation of these effects, aiming to comprehend the potential role of different electron-donating and electron-withdrawing substituents in lanthanide extraction and separation. These insights provide valuable guidelines for the rational design of DAPhen-based ligands for improved rare-earth element separations.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145336011","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}

{"title":"Formation of Distinct Isomers via Chemical Reaction in a Supersonic Jet: The Reaction of Sulfur Trioxide and Thioacetic Acid Studied by Rotational Spectroscopy.","authors":"Aaron J Reynolds, Kenneth J Koziol, Victor Drewanz, Luis R Padilla, Kenneth R Leopold","doi":"10.1021/acs.jpca.5c06025","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c06025","url":null,"abstract":"<p><p>The reaction between sulfur trioxide (SO₃) and thioacetic acid (thiol form, CH₃COSH) is studied by microwave spectroscopy in a supersonic jet. With multiple isotopic substitutions, and supported by MP2 and density functional theory calculations, the spectra unambiguously establish the formation of two distinct isomers. The first, denoted the O-S isomer, is CH₃C(=S)OSO₂OH and involves a new bond between the oxygen of the thioacetic acid and the sulfur of the SO₃. The second, denoted the S-S isomer, CH₃C(=O)SSO₂OH, involves the new bond between the sulfur of the acid and the sulfur of the SO₃. The O-S isomer is entirely analogous to the product identified in previous studies of the RCOOH + SO₃ and C₆H₅COSH + SO₃ reactions, but the formation of the S-S isomer is new. Calculations place the S-S isomer ∼8 kcal/mol lower in energy than the O-S form, suggesting that the latter is a kinetically controlled product. The mechanism by which the S-S isomer forms is unclear but may involve either a set of independent pathways or initial formation of the O-S isomer, followed by rapid rearrangement. Participation by a third body is likely. Without input from an external energy source, the formation of two isomers in a supersonic expansion is unusual.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145327884","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}

{"title":"Unveiling the Inverse Sandwich Cr₂B₆ Building Block for Self-Assembled Antiferromagnetic Nanowires in Cr₂B_<i>n</i> (<i>n</i> = 3-12) Clusters.","authors":"Kai Wang, Chaoyong Wang, Linyuan Lian, Shuai Xu","doi":"10.1021/acs.jpca.5c05159","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c05159","url":null,"abstract":"<p><p>Dual-transition-metal-doped boron clusters have garnered growing research interest owing to their unique bonding patterns and distinctive electronic/magnetic properties. In this work, we investigated the structural evolution, bonding characteristics, and electronic and magnetic properties of Cr₂B_<i>n</i> (<i>n</i> = 3-12) clusters through a hybrid global search algorithm and density functional theory calculations. It was found that small-sized Cr₂B_<i>n</i> (<i>n</i> = 3-5) clusters adopt quasi-planar structures; those with <i>n</i> = 6-8 form inverse sandwich configurations, while larger clusters (<i>n</i> = 9-12) exhibit extended inverse sandwich-based structures. In all Cr₂B_<i>n</i> (<i>n</i> = 3-12) clusters, the two Cr atoms exhibit opposite magnetic moments greater than 3 μ_B. The Cr₂B₆ cluster exhibits a considerable HOMO-LUMO gap (3.554 eV) and dual σ- and π-aromaticity, indicative of its high stability. Two self-assembled 1D nanowires derived from the inverse sandwich Cr₂B₆ structure are antiferromagnetic semiconductors that exhibit indirect and direct band gaps of 2.03 and 0.80 eV, respectively.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145336019","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}

{"title":"Mechanistic Insights into Chemoselectivity in Nickel-Catalyzed Arylation of Competitive Nucleophilic Systems: A DFT Perspective.","authors":"Chao Shan, Zhiqiang Zhang, Wanli Cheng, Xuexiang Ma, Ranran Li","doi":"10.1021/acs.jpca.5c04513","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c04513","url":null,"abstract":"<p><p>Nickel-catalyzed cross-coupling of alcohols or amines with aryl electrophiles enables the selective arylation of complex substrates bearing competing nucleophilic groups without resorting to protective groups. In this study, the mechanisms underlying such competitive arylation reactions are investigated using DFT calculations to elucidate the origins of chemoselectivity. The results identify reductive elimination as the rate-limiting step, with chemoselectivity primarily governed by kinetic control. The dominant factor influencing the selectivity in various contending alcohols is the steric hindrance around the hydroxyl O atom. Diols exhibit selective primary <i>O</i>-arylation due to stronger d-p interactions between the alkoxide and the nickel-bisphosphine fragment in both reactant intermediates and transition states. Steric hindrance predominantly dictates <i>O</i>- versus <i>N</i>-arylation selectivity when alcohols and arylamines compete, whereas both steric and electronic effects collectively determine the preference for <i>N</i>-arylation when alcohols compete with alkylamines. Moreover, the selective <i>O</i>-arylation of amino alcohols is attributed to stronger noncovalent interactions between C and O. These mechanistic insights facilitate developing selective arylation methodologies for competitive nucleophilic systems.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145327858","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}

{"title":"Spectroscopic Constants of Chiral Isomers of Acetamide.","authors":"Roger D Amos, Rika Kobayashi","doi":"10.1021/acs.jpca.5c04503","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c04503","url":null,"abstract":"<p><p>One of the major achievements of computational chemistry response theory is its ability to calculate atomic and molecular properties and, thus, aid experimentalists. Spectroscopists, in particular, have benefitted from theoretical modeling to help predict and interpret their spectra. In this paper, we continue previous work on providing highly accurate spectroscopic constants for interstellar molecules. We focus on the chiral isomers of acetamide, which are of particular interest for their speculated importance to the origins of life. In addition, we provide simulations of the VCD spectra of these molecules.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145327872","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}

{"title":"Atmospheric Temperature Dependence of β-Caryophyllene Ozonolysis Kinetics Is Governed by Stabilized Prereactive Complexes.","authors":"Hengjia Ou, Kunpeng Chen","doi":"10.1021/acs.jpca.5c05523","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c05523","url":null,"abstract":"<p><p>Atmospheric lifetime of volatile organic compounds (VOCs) is determined by oxidation kinetics, which is potentially sensitive to the change of temperature. However, the influence of temperature on the oxidation kinetics of large VOCs, such as sesquiterpenes, remains inadequately explored due to limited experimental data and insufficient accuracy of computations. In this study, we accurately simulate the temperature dependence (243-313 K) of ozonolysis kinetics of β-caryophyllene, a representative sesquiterpene in the atmosphere, by explicitly incorporating stabilized prereactive complexes (SPCs). Our results reveal that SPCs formed at the endocyclic C═C double bond primarily drive the temperature-dependent ozonolysis kinetics owing to their low energy barriers for forming primary ozonides (POZs). These endocyclic SPCs also exhibit a balance between the forward reaction and backward dissociation. In contrast, exocyclic SPCs, while more thermodynamically stable, are less reactive and tend to dissociate back into β-caryophyllene and ozone (O₃). This mechanistic difference may explain why O₃ cycloaddition at the endocyclic C═C double bond dominates the ozonolysis kinetics of β-caryophyllene, despite the lower relative abundance of endocyclic SPCs compared to the exocyclic SPCs. The computed kinetics exhibits a pre-exponential factor of 2.0 × 10^-15 cm³ molecule^-1 s^-1 and a negative activation energy of -4.4 kJ mol^-1. Our computed temperature dependence factor is 529.8 K^-1, which agrees with the experimental value (559 ± 97 K^-1) in previous measurements. The SPC-incorporated computation further supports the accurate prediction of the pseudo-first-order atmospheric lifetime at different temperatures. Overall, this study demonstrates that incorporating SPCs into computational models can provide an effective framework for simulating VOC oxidation kinetics and thus atmospheric lifetimes at the extreme temperatures in climate change.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145327882","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}

{"title":"Characterizing Infrared Spectra of OH^-·(H₂O)₂ and OH^-·(H₂O)₃ with Constrained Nuclear-Electronic Orbital Molecular Dynamics.","authors":"Zhe Liu, Yiwen Wang, Yuzhe Zhang, Nan Yang, Yang Yang","doi":"10.1021/acs.jpca.5c04334","DOIUrl":"10.1021/acs.jpca.5c04334","url":null,"abstract":"<p><p>The vibrational spectra of OH^-·(H₂O)_<i>n</i> clusters for small <i>n</i> have been well established experimentally, with fundamental modes largely assigned. However, clear assignment of highly anharmonic modes and combination bands associated with strong hydrogen bonds, which often manifest as broad spectral features, remains challenging. In this work, we employ constrained nuclear-electronic orbital molecular dynamics (CNEO-MD) to provide detailed peak assignments and plausible physical interpretations for the vibrational spectra of OH^-·(H₂O)_n clusters with <i>n</i> = 2 and 3. The CNEO framework incorporates nuclear quantum effects, particularly nuclear quantum delocalization, through the underlying effective potential energy surfaces. When combined with classical molecular dynamics, CNEO-MD further captures coupling effects between vibrational modes. Leveraging machine-learned potentials, we perform a series of temperature-dependent CNEO-MD simulations and use the resulting spectra to facilitate peak assignment. Our results largely confirm the experimental assignments reported by Johnson and coworkers [<i>J. Chem. Phys.</i> <b>2016</b>, 145, 134304], while also providing direct, physically grounded interpretations of previously unassigned features.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145318005","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}

{"title":"Using Topology to Predict Electrides in the Solid State.","authors":"Stefano Racioppi, Eva Zurek","doi":"10.1021/acs.jpca.5c05317","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c05317","url":null,"abstract":"<p><p>Electrides are characterized by electron density highly localized in interstitial sites, which do not coincide with direct interatomic contacts. The rigorous quantum mechanical definition of electrides is based upon topological criteria derived from the electron density, and in particular the presence of non-nuclear attractors (NNAs). We employ these topological criteria in combination with crystal structure prediction methods (the XtalOpt evolutionary algorithm), to accelerate the discovery of crystalline electrides at ambient and nonambient pressures. The localization and quantification of NNAs is used as the primary discriminator for the electride character of a solid within a multiobjective evolutionary structure search. We demonstrate the reliability of this approach through a comprehensive crystal structure prediction study of Ca₅Pb₃ at 20 GPa, a system previously theorized to exhibit electride character under compression. Our strategy could predict, and sort on-the-fly, several unknown low-enthalpy phases that possess NNAs in interstitial loci, such as the newly discovered <i>P</i>4/<i>mmm</i> structure. These results demonstrate how evolutionary algorithms, guided by rigorous topological descriptors, can be relied upon to effectively survey complex phases to find new electride candidates.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145311983","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}

{"title":"Occurrence and Impact of Electric-Field-Induced Discontinuities in Correlation Energies from Localized Pair-Natural-Orbital Methods.","authors":"Jose P Madriaga, T Daniel Crawford","doi":"10.1021/acs.jpca.5c05210","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c05210","url":null,"abstract":"<p><p>We report an investigation of discontinuities in the correlation energy produced by external static electric fields within the local pair-natural-orbital coupled-cluster singles and doubles (LPNO-CCSD) method. Such discontinuities arise as a result of variations in both the dimensions and character of the pairwise virtual-orbital domains resulting from changes in the strength of the field. Using several small-molecule test cases - water, fluoroethylene, hypofluorous acid and <i>cis</i>-1,3-butadiene we observe that, although the discontinuities in the correlation energy are small (typically 1 μ<i>E</i>_<i>h</i>), they can yield substantial errors in higher-order electric-field-dependent properties computed using finite-difference techniques. For the static hyperpolarizability (third derivative of the energy with respect to the field) of water, for example, the discrepancies between LPNO-CCSD and canonical-MO CCSD methods can exceed 100%. Furthermore, weak-field displacements that should normally decrease errors in numerical differentiation can yield orders-of-magnitude errors due to magnification of the energy discontinuities by small field-displacement denominators. For larger molecules, such fields can produce dramatic errors in the static polarizability (second derivative of the energy with respect to the field) and hyperpolarizability even with very tight PNO cutoffs. The use of basis sets containing diffuse functions, which are essential for reliable predictions of field-dependent response properties, tend to exacerbate the observed errors. In addition, the use of fixed virtual PNO dimensions does no resolve the problem due to mixing of the PNOs relative to zero-field orbitals as a result of large condition numbers of the pair-correlation densities.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306384","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}