International Journal of Quantum Chemistry最新文献

{"title":"Density Functional Study on the Structures and Adsorption Properties of PtAgn (n = 1–16) Clusters","authors":"Zhimei Tian,&nbsp;Dongyang He,&nbsp;Jingzhe Sun,&nbsp;Tao Zhang,&nbsp;Chongfu Song","doi":"10.1002/qua.70022","DOIUrl":"https://doi.org/10.1002/qua.70022","url":null,"abstract":"<div>\u0000 \u0000 <p>The structures and properties of PtAg_<i>n</i> (<i>n</i> = 1–16) clusters have been studied by density functional theory (DFT). The Tpssh/def2-TZVP method is chosen in this work. Calculations reveal that the structures of PtAg_<i>n</i> (<i>n</i> = 1–16) clusters are planar structures when <i>n</i> = 1–3, while they present three-dimensional structures when <i>n</i> = 4–16. The coordination number of the Pt atom in PtAg_<i>n</i> (<i>n</i> = 1–16) clusters are in the range of 1–11. Pt atoms in PtAg_<i>n</i> (<i>n</i> = 1–16) clusters prefer to locate in the centers of the structures. The electronic structures are compared with available experimental and theoretical data. The stability analysis manifests that the clusters have odd-even stability properties. The study of catalytic properties on PtAg_<i>n</i> (<i>n</i> = 1–16) clusters perform similar interactions with one CO molecule. The Pt atom favors interacting with the carbon terminal of the CO molecule. According to the thermodynamic property study, the adsorption reactions of PtAg_<i>n</i> (<i>n</i> = 1–16) and CO are all spontaneous. The stability of PtAg_<i>n</i>CO (<i>n</i> = 1–16) clusters present odd-even properties. The projected density of states (PDOS) study reveals that the orbital hybridization phenomenon is present between the Pt and C atoms in the PtAg₆CO cluster.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 5","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143455766","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring Graphitic Carbon Nitride as Novel Drug Delivery System for Hesperetin (Anticancer Drug): Insights From DFT Calculations and Molecular Dynamics Simulations","authors":"Mubashar Ilyas,&nbsp;Maroof Ahmad Khan,&nbsp;Shehwas Kalsoom,&nbsp;Muhammad Abbas,&nbsp;Mehvish Perveen,&nbsp;Javed Iqbal,&nbsp;Shabbir Muhammad,&nbsp;Hui Li","doi":"10.1002/qua.70018","DOIUrl":"https://doi.org/10.1002/qua.70018","url":null,"abstract":"<div>\u0000 \u0000 <p>In the present work, density functional theory (DFT) and molecular dynamics (MD) simulations were employed to explore the interaction between Hesperetin (HST), an anticancer drug, and 2D graphitic carbon nitride (GRP) nanocarrier designed for targeted drug delivery. The B3LYP/B3LYP-D3 functionals and the 6-31G (d,p) basis set were used for DFT calculations in both gaseous and solvent environments. The outcomes reveal exothermic adsorption (adsorption energy = −0.18 eV) of HST on the GRP nanocarrier, suggesting increased stability for enhanced drug delivery in biological systems. Calculations of orbital energy and density of state (DOS) demonstrate a reduced HOMO–LUMO energy gap (3.15 eV) of GRP upon interaction with HST. In an aqueous medium, the HST@GRP complex exhibits a higher dipole moment (3.48 D) compared to the gas phase (1.60 D), facilitating effective drug transportation. Charge decomposition analysis (CDA) identifies an orbital overlap between HST and GRP, supported by natural bond orbitals showing evidence of charge transfer. Computational UV–visible spectra closely match with experimental data. The elucidation of the photoinduced electron transfer (PET) mechanism explains fluorescence quenching. In summary, these findings suggest the potential of GRP as an efficient nanocarrier for HST drug delivery, encouraging further exploration of 2D nanomaterials in drug transport systems.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 5","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447004","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sustainable Synthesis, DFT, Docking and In Vitro Evaluation of 6-Mercaptopurine Syringic Acid Cocrystal: A Potent Drug for Breast Cancer Therapy","authors":"Thangamathi Rajendran,&nbsp;Azar Zochedh,&nbsp;Kaliraj Chandran,&nbsp;Bandar Ali Al-Asbahi,&nbsp;Yedluri Anil Kumar,&nbsp;Athimoolam Shunmuganarayanan,&nbsp;Asath Bahadur Sultan","doi":"10.1002/qua.70020","DOIUrl":"https://doi.org/10.1002/qua.70020","url":null,"abstract":"<div>\u0000 \u0000 <p>The 6-mercaptopurine syringic acid (6MPSY) a new drug–drug cocrystal has been synthesized by the neat grinding method. The prepared cocrystal 6MPSY has been screened by the powder x-ray diffraction procedure and the single phase was confirmed. Using density functional theory with B3LYP/6-311++G (d, p) source set, the structural parameters were computed and associated with the structural parameters of the 6-mercaptopurine molecule and syringic acid molecule reported earlier exhibit good agreement. Experimental FTIR and UV–vis spectra were documented to identify and analyze the group vibrational frequencies and electronic behavior of the cocrystal. The NBO study was accomplished and the inter- and intra-molecular interactions were established. The inspection of the topological (MEP, ELF, LOL) and non-covalent (RDG, IRI, DORI) contacts has exposed diverse groups of inter- and intra-molecular links on the source of electron localization density and color gauge pointer, respectively. Mulliken and natural atomic charges have been calculated and depicted. Fukui studies gave the reactive site with high <i>f</i>⁺ and <i>f</i>⁻ for C10, C17, C33, and H14 of the drug–drug cocrystal. The FMO analysis exhibits a low energy gap of 3.7612 eV that shows the efficiency of the drug–drug cocrystal in terms of chemical reactivity and stability. In addition, the thermodynamical parameters were calculated. The anti-breast cancer activity of 6MPSY was investigated through in silico and in vitro analysis. The docking outcomes of 6MPSY range between −7.5 and −9.3 kcal/mol, and the calculated IC₅₀ value in MDA-MB-231 breast cancer cells was 83.2 μg/mL.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 5","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447005","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical Insights of the Non-Rigid Behavior of Benzophenone by Franck-Condon Factors Approach","authors":"Rafael Flores-Larrañaga,&nbsp;María Eugenia Castro,&nbsp;Alejandro Palma,&nbsp;Francisco J. Melendez","doi":"10.1002/qua.70019","DOIUrl":"https://doi.org/10.1002/qua.70019","url":null,"abstract":"<div>\u0000 \u0000 <p>Benzophenone is a molecule with several extremely relevant characteristics, widely used as a type-2 photoinitiator due to its unique electronic properties and a very efficient intersystem crossing. In general, benzophenone can absorb directly to S₁ or S₂ states, but S₀ → S₁ transition is weak. Also, benzophenone has symmetric activity of the torsional modes of the phenyl groups, suggesting that is a non-rigid molecule. This work has two fundamental purposes. The first is to examine the ground state (S₀) and first singlet excited state (S₁) of benzophenone using TD-DFT methodology to generate the potential energy surface (PES) to understand its non-rigid behavior; and the second, to examine the Franck-Condon factors (FC factors) between the transition S₀ → S₁. From our results, the most accurate was the hybrid functional PBE0. From the PES analysis of S₀ and S₁ states, we observe that several minima were located and that they are separated by relative low energy barriers. The global minimum of S₀ is found at <i>θ</i>₁/<i>θ</i>₂ = 28.15° and for S₁ at <i>θ</i>₁/<i>θ</i>₂ = 20.71°. Interestingly, the PES of S₁ state shows a very extensive area of minimum energy and a local minimum located at <i>θ</i>₁ = 90.71°/<i>θ</i>₂ = 0.71°. From the vibrational spectra, we observe two intense signals that correspond to the symmetric phenyl twisting of normal mode 2 (2³ and 2⁴), and a combination between the symmetric hydrogen scissoring of 44¹ and 2³. As the vibronic spectrum tells, this transition is forbidden by the orbital theory but it is electronically allowed. Also, from the Duschinksy matrix, we observe a high mixing of vibrational modes.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 4","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143389023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DFT Investigations of Non-Toxic Perovskites RbZnX3 (X = F, Cl, and Br): Analyzing the Structural, Electrical, Optical, Mechanical, and Thermodynamic Properties for Suitable Optoelectronic Applications","authors":"Md. Bayjid Hossain Parosh,&nbsp;Mohshina Binte Mansur,&nbsp;Nusrat Jahan Nisha,&nbsp;Istiak Ahmed Ovi,&nbsp;Md. Jahirul Islam,&nbsp;Jehan Y. Al-Humaidi,&nbsp;Md. Rasidul Islam","doi":"10.1002/qua.70014","DOIUrl":"https://doi.org/10.1002/qua.70014","url":null,"abstract":"<div>\u0000 \u0000 <p>Comparative exploration of structural, population analysis, mechanical, electronic, optical, and magnetic properties of a zinc-based single, non-toxic, inorganic halide-based novel perovskite compound RbZnX₃ (X = F, Cl, and Br) without applying pressure by using GGA-PBE functional within the CASTEP code. Systematic investigations show mechanically stable compound with lattice parameters of the unit cell 4.25, 5.01, 5.50 Å, with indirect bandgaps of 3.637, 1.387, 0.103 eV for RbZnF₃, RbZnCl₃, and RbZnBr₃ respectively. Band gap data shows that RbZnX₃ is a semiconductor in nature, and RbZnCl₃ can be an ideal photovoltaic material. From CDD analysis, all three perovskites show a combination of metallic and ionic bonding. Computed optical properties ensure this compound is beneficial in PES and EUV-based applications, like- anti-reflection surface coating and optoelectronics like solar cells, and it can be a promising element in radiation shielding, spectroscopy, and biotech fields, as well as in high absorption and infrared sectors. High reflectivity makes them suitable as solar cell coating material. Mechanical properties ensure these studied elements' ductility, machinability, and anisotropy. Absorption and reflectivity diminish where energy loss is maximum. For being diamagnetic, it is for superconductors, electromagnetic shielding, and materials testing sectors. Moreover, this study focuses on various applications and possibilities of this compound. Materials are found ductile and RbZnF₃ has an excellent shear and bulk modulus. RbZnF₃ exhibits more significant fracture and plastic deformation resistance than RbZnCl₃ and RbZnBr₃. Moderate elasticity, flexibility, and strength make these suitable for various applications. The phonon calculation indicates that RbZnF₃ exhibits dynamic stability, whereas instability has been observed in RbZnCl₃ and RbZnBr₃. An increase in Debye temperature correlates with improved elastic modulus, elevated sound velocity, and higher melting temperature. RbZnBr₃ shows higher heat capacity at (<i>T</i> &lt; &lt; <i>θ</i>_D) and shows higher energy dispersion or entropy.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 4","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143380142","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structures and Electronic Properties of TMPb16−/0/+ (TM = Sc, Y, Ti, Zr, Hf) Clusters","authors":"Chaoyong Wang,&nbsp;Gan Yong,&nbsp;Yanbin Li,&nbsp;Fuhao Qi,&nbsp;Hanyu Du,&nbsp;Jun Zhao,&nbsp;Junji Guo,&nbsp;Kai Wang","doi":"10.1002/qua.70016","DOIUrl":"https://doi.org/10.1002/qua.70016","url":null,"abstract":"<div>\u0000 \u0000 <p>In this work, the structures and electronic properties of anionic, neutral, and cationic TMPb₁₆^−/0/+ (TM = Sc, Y, Ti, Zr, Hf) clusters were studied through a genetic algorithm (GA) code with density functional theory (DFT) calculations. The results show that anionic TMPb₁₆⁻ (TM = Sc, Y, Ti, Zr) and neutral TMPb₁₆ (TM = Ti, Zr, Hf) clusters adopt the Frank–Kasper (FK) polyhedron as the geometric structure, while TMPb₁₆ (TM = Sc, Y, Hf⁻) and all cationic states of these clusters prefer a fullerene-like bitruncated square trapezohedron. In these clusters, the gain and loss of electrons in transition metals (TM) are similar and very small, with only Hf atom as the electron donor. The average binding energy of cationic TMPb₁₆ is 0.02 and 0.1 eV higher than that of its anionic and neutral states, respectively. All these TMPb₁₆ (TM = Sc⁻, Y⁻, Ti, Zr, Hf) clusters with 68 electrons show superatomic features with the electronic shell configuration of (1S)²(1P)⁶(1D)¹⁰(1F)¹⁴(2S)²(1G)¹⁸(2P)⁶(2D)¹⁰ as same as that of TMSn₁₆ (TM = Sc⁻, Y⁻, Ti, Zr, Hf) clusters.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 4","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143370081","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unraveling Surface Chemistry of SnO2 Through Formation of Charged Oxygen Species and Oxygen Vacancies","authors":"Maliheh Shaban Tameh,&nbsp;Wayne L. Gladfelter,&nbsp;Jason D. Goodpaster","doi":"10.1002/qua.70017","DOIUrl":"https://doi.org/10.1002/qua.70017","url":null,"abstract":"&lt;p&gt;The ability of SnO&lt;sub&gt;2&lt;/sub&gt; surfaces to adsorb and activate oxygen species is essential for designing high-performance gas sensors and catalytic materials. In this study, density functional theory (DFT) calculations are employed to unravel the mechanisms governing oxygen adsorption on SnO&lt;sub&gt;2&lt;/sub&gt; (110) surfaces under varying surface conditions, including reduced, defective, and stoichiometric configurations. Our findings indicate various forms of charged oxygen species on the surface. The study reveals the presence of &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;O&lt;/mi&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{O}}_2^{2-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;, &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;O&lt;/mi&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{O}}_2^{-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;, and &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;O&lt;/mi&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{O}}^{2-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; on the reduced surface and &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msubsup&gt;\u0000 &lt;mi&gt;O&lt;/mi&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msubsup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{O}}_2^{2-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;, &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;O&lt;/mi&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {mathrm{O}}^{-} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;, and &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msup&gt;\u0000 &lt;mi&gt;O&lt;/mi&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msup&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 4","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70017","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143362940","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to Hydrostatic Pressure-Tuning of Opto-Electronic and Thermoelectric Properties Half-Heusler Alloy RhTiP With DFT Analysis","authors":"","doi":"10.1002/qua.70010","DOIUrl":"https://doi.org/10.1002/qua.70010","url":null,"abstract":"<p>A. Dixit, A. Saxena, J.A. Abraham, S. Dubey, R. Sharma, S.M.H. Qaid, I. Štich, M. Aslam, and A. Zetsepin, “Hydrostatic Pressure-Tuning of Opto-Electronic and Thermoelectric Properties Half-Heusler Alloy RhTiP With DFT Analysis,” <i>International Journal of Quantum Chemistry</i>, 124 (2024): e27482, https://doi.org/10.1002/qua.27482.</p><p>The author affiliation for Saif M. H. Qaid originally published without including the correct information. The affiliation should have been as follows:</p><p>⁶Department of Physics &amp; Astronomy, College of Science, King Saud University, Riyadh, Saudi Arabia.</p><p>In addition, the King Saud University funding information had the wrong identification number and should have been as follows:</p><p><b>Funding:</b> This research was supported by King Saud University (RSPD2024R762).</p><p>We apologize for the error.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 3","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70010","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143111568","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pyrolysis Kinetics of Polytetrafluoroethylene (PTFE)","authors":"Yongjin Wang,&nbsp;Shengkai Wang,&nbsp;Qingzhao Chu,&nbsp;Dongping Chen","doi":"10.1002/qua.70015","DOIUrl":"https://doi.org/10.1002/qua.70015","url":null,"abstract":"<div>\u0000 \u0000 <p>Polytetrafluoroethylene (PTFE) is widely used in fields such as propellants and flame retardants. However, this is still a vacancy of detailed kinetic mechanisms to describe the complete decomposition of PTFE in the gas phase. The current work addresses this issue by conducting ab initio calculations for key reactions involved in the PTFE pyrolysis system. The potential energy surfaces (PESs) of PTFE unimolecular and bimolecular reactions are determined at the DLPNO-CCSD(T)/cc-pVTZ//B3LYP-D3/6–31++G(d,p) level. Rate constants and branching ratios of the main reaction pathways are calculated by solving the RRKM master equation, and the thermochemical properties of related species at the DLPNO-CCSD(T)/CBS level are calculated via the atomization method. The current study found that the initial decomposition of PTFE is dominated by the C<span></span>C scission reactions and free radical (H, OH, CF, CF₂, and CF₃) abstraction reactions, forming the corresponding free radical species. Further β-C<span></span>C scission reactions dominate the overall kinetics and continuously generate CF₂CF₂. Self-decomposition and free radical–driven decomposition of PTFE produce small molecules such as HF, FOH, CF₂, CF₃, and CF₄. This work provides quantitative predictions of the detailed decomposition reaction pathways of gas-phase PTFE and will lay a solid foundation for the development of detailed kinetic mechanisms for PTFE combustion and degradation.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 3","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143111163","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to “The hyper-Wiener index of diamond nanowires”","authors":"","doi":"10.1002/qua.27514","DOIUrl":"https://doi.org/10.1002/qua.27514","url":null,"abstract":"&lt;p&gt;\u0000 &lt;span&gt;B. Nagy&lt;/span&gt;, “ &lt;span&gt;The Hyper-Wiener Index of Diamond Nanowires&lt;/span&gt;,” &lt;i&gt;International Journal of Quantum Chemistry&lt;/i&gt; &lt;span&gt;124&lt;/span&gt;, no. &lt;span&gt;1&lt;/span&gt; (&lt;span&gt;2024&lt;/span&gt;): e27258.&lt;/p&gt;&lt;p&gt;There is a miscalculation in the above paper; the correct formula and value of hyper-Wiener indices are presented here. The numbering is from the original article; the correct versions of the equations with the corrected proof can be found below.&lt;/p&gt;&lt;p&gt;Now we state our main results.&lt;/p&gt;&lt;p&gt;\u0000 &lt;/p&gt;&lt;p&gt;\u0000 &lt;/p&gt;&lt;p&gt;\u0000 &lt;/p&gt;&lt;p&gt;Some of the first elements of the sequence defined above give the hyper-Wiener index of relatively small diamond grid samples, that is, &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mi&gt;W&lt;/mi&gt;\u0000 &lt;mi&gt;W&lt;/mi&gt;\u0000 &lt;mo&gt;(&lt;/mo&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mi&gt;G&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;1&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;\u0000 &lt;mo&gt;)&lt;/mo&gt;\u0000 &lt;mo&gt;=&lt;/mo&gt;\u0000 &lt;mn&gt;460&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ WWleft({G}_1right)=460 $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;, &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mi&gt;W&lt;/mi&gt;\u0000 &lt;mi&gt;W&lt;/mi&gt;\u0000 &lt;mo&gt;(&lt;/mo&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mi&gt;G&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;2&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;\u0000 &lt;mo&gt;)&lt;/mo&gt;\u0000 &lt;mo&gt;=&lt;/mo&gt;\u0000 &lt;mn&gt;3556&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ WWleft({G}_2right)=3556 $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;, &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mi&gt;W&lt;/mi&gt;\u0000 &lt;mi&gt;W&lt;/mi&gt;\u0000 &lt;mo&gt;(&lt;/mo&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mi&gt;G&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;3&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msub&gt;\u0000 &lt;mo&gt;)&lt;/mo&gt;\u0000 &lt;mo&gt;=&lt;/mo&gt;\u0000 &lt;mn&gt;14&lt;/mn&gt;\u0000 &lt;mspace&gt;&lt;/mspace&gt;\u0000 &lt;mn&gt;306&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ WWleft({G}_3right)=14kern0.2em 306 $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;, &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mi&gt;W&lt;/mi&gt;\u0000 &lt;mi&gt;W&lt;/mi&gt;\u0000 &lt;mo&gt;(&lt;/mo&gt;\u0000 &lt;msub&gt;\u0000 &lt;mrow&gt;\u0000 ","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 3","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.27514","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143110477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}