International Journal of Quantum Chemistry最新文献

{"title":"On the Validity of Atomic Charges as Reactivity Descriptors: Bridging Conceptual Density Functional Theory With Information-Theoretic Approach in Transition-Metal Catalysis","authors":"Wenbiao Zhang,&nbsp;Shichao Ma,&nbsp;Zile Zhang,&nbsp;Xuehui Li,&nbsp;Wentao Mu,&nbsp;Shubin Liu","doi":"10.1002/qua.70249","DOIUrl":"https://doi.org/10.1002/qua.70249","url":null,"abstract":"<div>\u0000 \u0000 <p>Atomic charges are widely used as intuitive measures of chemical reactivity, yet their theoretical validity as quantitative descriptors remains unclear. In this work, we examine the relationship between global reactivity indices from conceptual density functional theory (CDFT) and local atomic charges derived from the information-theoretic approach (ITA), using NO_x intermediates coordinated to Mn⁴⁺ centers involved in the selective catalytic reduction of NO_x as a model system. Strong linear correlations are observed between Hirshfeld charges on oxygen atoms and CDFT descriptors, including electron affinity and electrophilicity index, demonstrating that atomic charges can quantitatively represent electrophilicity and nucleophilicity at true reaction centers. Benchmark analysis further shows that Hirshfeld charge uniquely preserves this equivalence among common charge schemes. In contrast, charges on nitrogen atoms exhibit volcano-type relationships with CDFT reactivity indices, indicating a breakdown of descriptor validity when an atomic site is not directly involved in the reaction. Analysis of electronic structure properties reveals that this apparent scaling originates from the underlying Mn 3d states, rather than the intrinsic reactivity of the nitrogen site. These results establish a clear criterion for the validity of atomic charges as reactivity descriptors and provide a density-based framework bridging CDFT and ITA for understanding and designing transition-metal catalytic systems.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 13","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148274719","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":"Li2B8 Featuring Dynamic Fluxionality and High-Capacity Hydrogen Storage: Insights From Density Functional Theory","authors":"Da-Zhi Li,&nbsp;Ling Pei,&nbsp;Li-Juan Zhang","doi":"10.1002/qua.70241","DOIUrl":"https://doi.org/10.1002/qua.70241","url":null,"abstract":"<div>\u0000 \u0000 <p>The planar B₈ disk can serve as an inorganic ligand to form boron-based metallic complexes. Here, we present a DFT study on the structural characteristics and hydrogen storage capacity of the Li₂B₈ binary cluster. The global minimum, <i>C</i>_<i>s</i><i>-</i>symmetric Li₂B₈ exhibits remarkable dynamic fluxionality at room temperature (300 K), with an approximately perpendicular Li₂ dimer freely sliding or rotating along a circular track on the B₈ platform, even without direct Li–Li interaction. The energy barrier for intramolecular rotation is only 0.02 kcal·mol⁻¹ at the single-point CCSD(T) level. Each Li site in the Li₂B₈ complex can store up to six H₂ molecules, reaching a gravimetric capacity of 19.05 wt%. The average adsorption energies per H₂ are 0.10–0.18 eV at the ωB97XD level, suggesting ideal reversibility for hydrogen storage and release, as confirmed by Born-Oppenheimer molecular dynamics simulations. These DFT insights identify the dilithium-doped boron nanostructure as a promising candidate for ultra-high hydrogen storage materials under ambient conditions.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 12","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148281936","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":"Dehydrogenative Coupling of Hydrosilanes With Alcohols and Amines: A Concerted Asynchronous Mechanism With an Early Hidden Reaction Intermediate","authors":"Imen Abidli,&nbsp;Sheila A. Martín,&nbsp;Bahoueddine Tangour,&nbsp;Abdelhamid Sayari","doi":"10.1002/qua.70245","DOIUrl":"https://doi.org/10.1002/qua.70245","url":null,"abstract":"<p>The dehydrogenative coupling of hydrosilanes with protic nucleophiles offers a promising route for hydrogen generation under mild conditions with no added catalysts. The current work is a theoretical investigation of the cross coupling of hydrosilanes and methanol, methylamine and 2-(methylamino)-ethanol (MEA), with particular emphasis on the reaction mechanism and consecutive hydride substitutions by the O- and N-containing groups of MEA, in the presence of Ph_4-nSiH_n with <i>n</i> = 1 to 4. We employed the density functional theory (DFT) and the intrinsic reaction coordinate (IRC) technique to delineate the energy profiles and the associated reaction mechanism. All nucleophilic substitutions were found to follow a concerted asynchronous mechanism involving a hidden reaction intermediate (HRI), which occurs prior to a pentacoordinated silicon transition state. This mechanism indicates that the Si<span></span>O bond formation and Si<span></span>H bond cleavage precede the H<span></span>H bond formation. This finding was refined by the reactive internal reaction coordinates (RIRC) analysis. For all Ph_4-nSiH_n silanes, successive (O<span></span>) substitutions corresponded to decreasing activation energy, indicating that the reaction became increasingly more favorable. For example, the activation energies decreased from 17.30 to 14.94 kcal mol⁻¹ for consecutive (O<span></span>) substitutions in PhSiH₃. In contrast, substitutions by (N<span></span>) groups showed the opposite trend, with activation barriers increasing as more nitrogen-containing ligands were introduced. These findings provide a molecular-level understanding of experimental data reported in the literature.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 12","pages":""},"PeriodicalIF":2.0,"publicationDate":"2026-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70245","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148237905","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":"Guidelines for Calculating the Enthalpies of Formation of Diazonium Salts","authors":"D. V. Khakimov,&nbsp;A. A. Voronin,&nbsp;L. L. Fershtat","doi":"10.1002/qua.70243","DOIUrl":"https://doi.org/10.1002/qua.70243","url":null,"abstract":"<div>\u0000 \u0000 <p>An approach to determining the enthalpies of formation of diazonium salts has been identified, which provides three alternative ways to establish the co-crystallizing agent in the method. Due to the virtual absence of experimental data, the method was additionally tested by an additive approach, for which cationic contributions for 15 different diazonium structures were determined. Nitrate salts with these diazonium cations exhibit enthalpies of formation ranging from −1.65 to 40.73 kcal mol⁻¹ for calculations involving nitrogen release from the neutral structure and from 33.16 to 74.9 kcal mol⁻¹ when considering the neutral diazo compound. The final decision on the approach can be determined by either experimental value.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 12","pages":""},"PeriodicalIF":2.0,"publicationDate":"2026-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148237904","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":"Oxoaporphine-Metformin Rhodium(III) Hybrid Ionic Complex With Antidiabetes and Anticancer Effects: New Insights From DFT Computations","authors":"Costantino Zazza,&nbsp;Nico Sanna,&nbsp;Felice Grandinetti","doi":"10.1002/qua.70244","DOIUrl":"https://doi.org/10.1002/qua.70244","url":null,"abstract":"<p>A recently proposed (<i>J. Am. Chem. Soc.</i> <b>2025</b>, <i>147</i>, 45 145) dual antidiabetic and anticancer metallodrug, obtained through the rational integration of the glucose-modulating agent metformin (Met) with a bioactive oxoaporphine alkaloid in the form of novel rhodium(III) complexes (<b>Rh-Met</b>) is investigated—for the first time—within the Density Functional Theory (DFT) framework using the Generalized Gradient Approximation (GGA). Supramolecular contacts stabilizing the [Rh(L¹)Cl₄]⁻/[Rh(L¹)(Met)Cl₂]⁺ ionic pair, which constitutes the <b>Rh-Met</b> drug in its crystallographic packing, are investigated by combining Quantum Theory of Atoms in Molecules (QTAIM) descriptors with the Independent Gradient Model based on Hirshfeld Partition (IGMH) visual analysis of intramolecular and intermolecular interactions. A comprehensive view, based on quantum mechanics (QM), is then provided about the nature of the mutual chemical interactions finely modulating the observed self-assembly in the deposited X-ray structure.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 12","pages":""},"PeriodicalIF":2.0,"publicationDate":"2026-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70244","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148237758","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":"Effect of Endohedral Doping in the C84 Cage on Superatom Molecular Orbitals","authors":"Padmavathy Venkatakrishnan,&nbsp;Vijayakumar S","doi":"10.1002/qua.70240","DOIUrl":"https://doi.org/10.1002/qua.70240","url":null,"abstract":"<div>\u0000 \u0000 <p>Exploring Superatom Molecular Orbitals (SAMOs) nearer to the Fermi level in higher fullerenes systematically provides a vital path to many molecular electronic applications. In this study, using DFT, the SAMO states of pristine and endohedrally doped C₈₄ derivatives with metal atoms such as Sc, Ti, V, Cr, Mn, Fe, and Co at different sites inside the cage are investigated in both their molecular and periodic forms. As anticipated, C₈₄ derivatives are observed with lower SAMO energy, and the lowest value of ∼1.0 eV was exhibited by the Mn-doped derivative in both molecular and periodic forms. The charge transfer infers that the endohedrally doped metal atoms have significantly influenced the SAMO distribution in the cage. Furthermore, the band structure reveals the effect of endohedral doping on the strong dispersion of delocalized bands in the higher energy range, which interprets the overlap of the spatial wavefunctions with neighboring molecules. Hence, this study demonstrates how the nature, confinement, and energy of SAMOs near the Fermi level open new prospects for many charge transport applications in higher fullerene derivative-based systems.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 12","pages":""},"PeriodicalIF":2.0,"publicationDate":"2026-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148237672","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":"Seniority-Zero Quadratic Canonical Transformation Theory","authors":"Daniel F. Calero-Osorio,&nbsp;Paul W. Ayers","doi":"10.1002/qua.70215","DOIUrl":"https://doi.org/10.1002/qua.70215","url":null,"abstract":"<p>We propose a method to solve the Schrödinger equation for systems with static/strong electron correlation using Hamiltonian transformations. Building on our previous work on seniority-zero canonical transformation theory, which seeks a unitary transformation that maps the Hamiltonian into the seniority-zero space, this method presents an alternative way of evaluating the Baker–Campbell–Hausdorff (BCH) expansion based on quadratic canonical transformation theory. The extension aims to relax the small-generator constraint by allowing approximate four-body contributions in the expansion, thus expanding the class of excitations previously allowed in SZ-LCT, where only approximate three-body operators were retained. Numerical tests reveal that the seniority-zero quadratic canonical transformation method (SZ-QCT) delivers good accuracy, with most errors within chemical accuracy. In particular, SZ-QCT shows sub-milli Hartree errors in cases where larger generators are needed to recover the residual dynamic correlation. The computational scaling of SZ-QCT is the same as that of SZ-LCT, <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>O</mi>\u0000 <mfenced>\u0000 <mrow>\u0000 <msup>\u0000 <mi>N</mi>\u0000 <mn>8</mn>\u0000 </msup>\u0000 <mo>/</mo>\u0000 <msub>\u0000 <mi>n</mi>\u0000 <mi>c</mi>\u0000 </msub>\u0000 </mrow>\u0000 </mfenced>\u0000 </mrow>\u0000 <annotation>$$ mathcal{O}left({N}^8/{n}_cright) $$</annotation>\u0000 </semantics></math>, where <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <msub>\u0000 <mi>n</mi>\u0000 <mi>c</mi>\u0000 </msub>\u0000 </mrow>\u0000 <annotation>$$ {n}_c $$</annotation>\u0000 </semantics></math> is the number of cores available for the computation.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 12","pages":""},"PeriodicalIF":2.0,"publicationDate":"2026-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70215","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148174546","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":"A Renewed Vision for the International Journal of Quantum Chemistry","authors":"Shubin Liu","doi":"10.1002/qua.70213","DOIUrl":"https://doi.org/10.1002/qua.70213","url":null,"abstract":"","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 12","pages":""},"PeriodicalIF":2.0,"publicationDate":"2026-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148174547","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":"Comprehensive Analysis of Aluminum-Substituted Lithium Nano Ferrites Using Experimental and DFT Approaches","authors":"Mohd. Hashim,&nbsp;Mukhlis M. Ismail,&nbsp;Shameran Jamal Salih,&nbsp;Mohd Sajid Ali,&nbsp;Hamad A. Al-Lohedan,&nbsp;Fahim Parvez,&nbsp;Nazmul Hasan,&nbsp;Alamgir Kabir,&nbsp;Khalid Umar,&nbsp;Amos Nhlapo","doi":"10.1002/qua.70224","DOIUrl":"https://doi.org/10.1002/qua.70224","url":null,"abstract":"<p>The sol–gel auto-combustion approach prepared compounds of aluminum-substituted lithium ferrites nanocrystalline (Li_0.5Al_<i>x</i>Fe_{2.5−<i>x</i>}O₄, where <i>x</i> = 0.0–0.8, step 0.2). X-ray diffraction (XRD) investigation validated the cubic phase spinel structure and revealed that the lattice constant altered drastically, particularly for the sample <i>x</i> = 0.6, which reduced dramatically, while the crystallite size decreased and reached roughly 5 nm for sample <i>x</i> = 0.8. The variation of the electronic structure leads to a change in the band gap of LiAl ferrite due to the replacement of Al by Li ferrite with distinct electronic configurations. The Spin-polarized Density Functional Theory (DFT) simulation was performed to demonstrate the electronic and optical properties of the Li-Al ferrites. The lattice parameters of the optimized structures and the band gap were consistent with the experimental data. A noticeable band gap was observed, and anisotropy was found in the spin contributions of the band structure and density of states, demonstrating the potential of lithium ferrites for photovoltaic and spintronic applications.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 11","pages":""},"PeriodicalIF":2.0,"publicationDate":"2026-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70224","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148174166","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":"Comprehensive Analysis of Aluminum-Substituted Lithium Nano Ferrites Using Experimental and DFT Approaches","authors":"Mohd. Hashim,&nbsp;Mukhlis M. Ismail,&nbsp;Shameran Jamal Salih,&nbsp;Mohd Sajid Ali,&nbsp;Hamad A. Al-Lohedan,&nbsp;Fahim Parvez,&nbsp;Nazmul Hasan,&nbsp;Alamgir Kabir,&nbsp;Khalid Umar,&nbsp;Amos Nhlapo","doi":"10.1002/qua.70224","DOIUrl":"https://doi.org/10.1002/qua.70224","url":null,"abstract":"<p>The sol–gel auto-combustion approach prepared compounds of aluminum-substituted lithium ferrites nanocrystalline (Li_0.5Al_<i>x</i>Fe_{2.5−<i>x</i>}O₄, where <i>x</i> = 0.0–0.8, step 0.2). X-ray diffraction (XRD) investigation validated the cubic phase spinel structure and revealed that the lattice constant altered drastically, particularly for the sample <i>x</i> = 0.6, which reduced dramatically, while the crystallite size decreased and reached roughly 5 nm for sample <i>x</i> = 0.8. The variation of the electronic structure leads to a change in the band gap of LiAl ferrite due to the replacement of Al by Li ferrite with distinct electronic configurations. The Spin-polarized Density Functional Theory (DFT) simulation was performed to demonstrate the electronic and optical properties of the Li-Al ferrites. The lattice parameters of the optimized structures and the band gap were consistent with the experimental data. A noticeable band gap was observed, and anisotropy was found in the spin contributions of the band structure and density of states, demonstrating the potential of lithium ferrites for photovoltaic and spintronic applications.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 11","pages":""},"PeriodicalIF":2.0,"publicationDate":"2026-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70224","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148174241","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}