The Journal of Physical Chemistry A最新文献

{"title":"Modeling Structural and Optical Properties of 6,6,12-Graphyne Oligomer Fragments.","authors":"Andreas Erbs Hillers-Bendtsen, Frederik Ørsted Kjeldal, Nicolai Machholdt Høyer, Kurt V Mikkelsen","doi":"10.1021/acs.jpca.5c01540","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c01540","url":null,"abstract":"<p><p>This study investigates the structural and optical properties of 6,6,12-graphyne by analyzing five different radiaannulene oligomer fragments of the two-dimensional (2D) sheet in vacuum, cyclohexane, dichloromethane, and toluene. These properties are examined using various density functional theory (DFT) methods in combination with different basis sets. Solvent effects are incorporated using the integral equation formalism polarizable continuum model (IEF-PCM). The findings indicate that structural properties are primarily influenced by the inclusion of exact Hartree-Fock exchange in the chosen DFT method and the presence of polarization functions in the applied basis sets. For optical properties, all five molecules absorb light across the visible spectrum through both one- and two-photon processes. Notably, the inclusion of range correction in the selected method significantly alters the optical characteristics making alignment with experiment and CC2 (Coupled Cluster with Singles and approximate Doubles) calculations better. The presence of a solvent is found to enhance both infrared and ultraviolet-visible (UV-vis) absorption, while enforcing a planar geometry on the systems has minimal impact on the observed properties. Finally, comparisons with experimental spectra confirm that the calculations accurately reproduce key features and trends in the experimental data.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342136","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":"A Mechanistic Study on the Synthesis Reaction of Glycerol Sulfite─A Key Intermediate for Novel Electrolyte Additives.","authors":"Honghua Xu, Weiya Zhang, Yiwen Shen, Lu Yu, Qiang Wang","doi":"10.1021/acs.jpca.5c04978","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c04978","url":null,"abstract":"<p><p>Using SO₂ as a sulfinic-acid building block to synthesize valuable sulfur-based electrolyte additives is an important issue in the field of green and sustainable chemistry. Glycerol sulfite, as a key intermediate for the design and synthesis of sulfite-based electrolyte additives, clarifying its synthesis mechanism is of great significance for the design and synthesis of sulfite-based additives. Herein, the reaction mechanisms of synthesizing glycerol sulfite were explored by density functional theory (DFT) calculations, based on an analysis of glycerol sulfite's structures and properties. The results show that the reaction of SOCl₂ with glycerol proceeds through two steps and removes two molecules of HCl, generating glycerol sulfite. The first step of removing HCl is the rate-determining step, with an activation energy barrier of 36.97 kcal/mol. Based on this, we proposed an innovative green synthetic strategy for the atom-economical synthesis of glycerol sulfite by the direct reaction of SO₂ with glycerol. The reaction of the SO₂ with glycerol involves three steps and removes one molecule of H₂O to form glycerol sulfite. The formation of the S-O bond in the second step is the rate-determining step. The activation energy barrier was reduced to 29.75 kcal/mol, which is better than the reaction of SOCl₂ with glycerol to form glycerol sulfite. Further exploration of the three-molecule synergistic reaction of 2-cyanopyridine, SO₂, and glycerol revealed that glycerol sulfite was generated through four steps. The second step, where the cyano group of 2-cyanopyridine was transformed into an imide group, was identified as the rate-determining step, with an activation energy barrier as low as 25.51 kcal/mol, which was better than the reactions of SOCl₂ with glycerol and SO₂ with glycerol to form glycerol sulfite. These results provide a new avenue for the design and synthesis of sulfur-based electrolyte additives.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342132","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":"Evaluation of Density Functionals for Si-O-C-H Molecule Thermochemistry.","authors":"Ingeborg-Helene Svenum, Francesca Lønstad Bleken, Stefan Andersson","doi":"10.1021/acs.jpca.5c04844","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c04844","url":null,"abstract":"<p><p>The energies and vibrational frequencies of molecular species with Si-O-C-H compositions have been calculated at the CCSD(T) level (coupled cluster with single and double excitations and a perturbative treatment of triple excitations). The CCSD(T) results compare well with experimental data where the difference in enthalpy of formation is typically only about 1-2 kJ/mol in most cases. In addition, the same molecules have been calculated with density functional theory (DFT) calculations using nine commonly used density functionals and two different basis sets. The performance of the DFT calculations is compared with the CCSD(T) benchmark values in terms of enthalpy of formation, reaction energy, vibrational frequencies, and zero-point energies. The results show that the M06-2X functional provides the lowest mean absolute error (MAE) in terms of the enthalpy of formation, whereas, for the vibrational frequencies and zero-point energies, the SCAN functional gives the lowest MAE values. The results were also grouped according to the types of bonds that are present in the molecules. Moreover, an elaborate set of possible reactions within the molecular species in the Si-O-C-H system is included to evaluate the performance of the different DFT functionals with respect to the relative stability of species within the same reaction system. In this case, the B2GP-PLYP functional shows the smallest errors. PW6B95 is the functional that most consistently performs well for the studied properties of the included molecules. The coupled cluster data sets provide new benchmark data, several of which are not previously available for silicon chemistry.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342134","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":"PySIDT: Subgraph Isomorphic Decision Trees for Molecular Property Prediction.","authors":"Matthew S Johnson, Hao-Wei Pang, Anna C Doner, William H Green, Judit Zádor","doi":"10.1021/acs.jpca.5c04483","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c04483","url":null,"abstract":"<p><p>Accurate molecular property prediction is important across all fields of chemistry. Deep neural networks (DNNs) have become increasingly popular due to their ability to train automatically, avoiding the incredibly tedious process of constructing and extending traditional property estimation schemes. However, DNNs require large amounts of training data, are challenging to interpret, require large amounts of memory to load even during inference, and have severe difficulties incorporating qualitative chemical knowledge, which are often desired for molecular property prediction tasks. Here we present PySIDT (https://github.com/zadorlab/PySIDT), a software for training and running inference on Subgraph Isomorphic Decision Trees (SIDTs). SIDTs are graph-based decision trees made of nodes associated with molecular substructures. Inference is done by descending target molecular structures down the decision tree to nodes with matching subgraph isomorphic substructures and making predictions based on the final (most specific) nodes matched. SIDTs scale down well to dataset sizes much smaller than is feasible for DNNs. As trees of molecular substructures, SIDTs are inherently readable and easy to visualize, making them easy to analyze. They are also straightforward to extend and retrain, facilitate uncertainty estimation, and enable easy integration of expert knowledge. We demonstrate the SIDT approach discussing its application to a diverse range of molecular prediction tasks: rate coefficient estimation, diffusion coefficient estimation, thermochemistry estimation, transition state bond stretch prediction, p<i>K</i>_a prediction, stability of molecular structures, stability of surface structures, and prediction of surface lateral interaction energetics. Additionally, we demonstrate the power of the SIDT algorithms in two direct learning curve vanilla comparisons with the popular DNN-based software Chemprop and the popular gradient boosted trees-based software XGBoost on enthalpy of formation and rate coefficient prediction tasks. In particular, in the enthalpy of formation case, vanilla PySIDT is able to outperform vanilla Chemprop and XGBoost across the full range of training/validation set sizes out to 11,560 data points.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342138","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":"First-Principles Molecular Dynamics Simulations of Infrared and Raman Vibrational Spectra of H₅O₂⁺, D₅O₂⁺, DH₄O₂⁺, and D₄HO₂⁺ from 50 to 300 K.","authors":"Oluwaseun Omodemi, Martina Kaledin","doi":"10.1021/acs.jpca.5c05184","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c05184","url":null,"abstract":"<p><p>We report molecular dynamics simulations of infrared (IR) and Raman spectra of H₅O₂⁺ and its deuterium-substituted analogs. We use the well-tested HBB potential and dipole surfaces along with a recently fitted polarizability surface of CCSD(T)/aug-cc-pVTZ quality. The focus of the present work is to provide new insights into the O···O stretch region, located in the [500-700] cm^-1 spectral range, by means of analyzing the spectra over a broad range of temperatures: from 50 to 300 K. Also, rovibrational thermal averaging was performed to untangle the unusually complex spectra of partially deuterated isotopologues DH₄O₂⁺ and D₄HO₂⁺ with H and D minority species in both internal (int) and external (ext) positions. Our findings show that DH₄O₂⁺ (ext) is at least 90% prevalent at the [50-300] Kelvin temperatures, predominantly due to its low zero-point energy (ZPE). Furthermore, contrary to previous reports that the mixed isotopologue D₄HO₂⁺ (int) should be favored over D₄HO₂⁺ (ext) due to its lower ZPE, the present calculations indicate that while the D₄HO₂⁺ (ext) species is \"invisible\" at lower temperatures, it overtakes D₄HO₂⁺ (int) as the dominant species at 84.9 K and higher.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145342135","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":"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}