International Journal of Quantum Chemistry最新文献

{"title":"Origin of Transition Metal Binding Preferences in Pyridinic and Pyrrolic Nitrogen-Doped Graphene Single-Atom Catalysts","authors":"Angelina N. van Dam,&nbsp;Pascal Vermeeren","doi":"10.1002/qua.70301","DOIUrl":"https://doi.org/10.1002/qua.70301","url":null,"abstract":"<p>Transition metal-anchored nitrogen-doped graphene single-atom catalysts (SACs) have emerged as promising catalysts that combine the advantages of both homogeneous and heterogeneous catalysis. Two common vacancy motifs in nitrogen-doped graphene-based SACs are the pyridinic and pyrrolic vacancy sites. Despite their importance for catalyst design, quantitative insights into the intrinsic differences in their metal–support bonding interactions and their impact on the preferred metal binding site are still lacking. Here, we have quantum chemically investigated the trends in bonding interactions between Period 4 transition metals (TM = Ti, V, Cr, Mn, Fe Co, Ni, Cu, and Zn) and these vacancy motifs using relativistic, dispersion-corrected periodic density functional theory in combination with the activation strain model and Kohn-Sham molecular orbital (KS-MO) analyses. Regardless of the vacancy motif, the metal–support interaction follows the same trend across Period 4, namely a strengthening from Ti to Ni followed by a weakening from Ni to Zn. This trend originates from the interplay between the increasing effective nuclear charge and the gradual filling of the metal's 3<i>d</i> atomic orbitals. Additionally, the vacancy motif plays a key role in determining the preferred transition metal binding site. Ti and V preferentially bind to the larger pyrrolic vacancy site because the planar coordination minimizes Pauli repulsion between the TM and the support. In contrast, Cr through Zn favor the pyridinic motif, where shorter TM<span></span>N bonds and a larger C<span></span>N<span></span>C angle enhance both electrostatic and orbital interactions. Together, these insights could aid in the rational design of future SACs.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 20","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70301","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149177455","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":"Fractional Nikiforov-Uvarov Formalism for Dunkl-Schrödinger Equation With Deng-Fan Molecular Model","authors":"H. I. Alrebdi,&nbsp;U. S. Okorie,&nbsp;E. S. William,&nbsp;A. N. Ikot","doi":"10.1002/qua.70299","DOIUrl":"https://doi.org/10.1002/qua.70299","url":null,"abstract":"<p>The effect of Dunkl deformation parameters on the energy eigenvalues of the Deng-Fan potential is evaluated in this study. The conformable fractional Nikiforov-Uvarov method is employed to obtain the eigensolutions by solving the nonrelativistic Dunkl Schrödinger equation. The Pekeris approximation scheme is used to check the centrifugal barrier term. In addition, the energy solutions of Deng-Fan potential are obtained in the Minkowski space-time and without the Dunkl deformation parameter, as special cases. Energy eigenvalues for the selected diatomic molecules are seen to be significantly influenced by the Dunkl deformation parameter, fractional parameter, kinetic pre-factor and quantum state values considered. Our numerical results are also supported with graphical illustrations, which are discussed extensively.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 19","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70299","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149145573","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":"Dual Regulatory Mechanism of Intrinsic Electronegativity and Extrinsic Solvent Polarity for Excited-State Proton Transfer of BPDI Derivatives","authors":"Chang Liu,&nbsp;Zibo Shen,&nbsp;Junji Han,&nbsp;Jiahe Chen,&nbsp;Jinfeng Zhao","doi":"10.1002/qua.70300","DOIUrl":"https://doi.org/10.1002/qua.70300","url":null,"abstract":"<div>\u0000 \u0000 <p>This study conducts theoretical simulations to explore the synergistic regulation of chalcogen-substituent electronegativity and solvent polarity on the excited-state proton transfer (ESPT) behavior of three BPDI derivatives (BPDI-O, BPDI-S, BPDI-Se) and clarify the microscopic mechanisms of their excited-state double proton transfer (ESDPT). Geometric parameter statistics and infrared spectral analysis were performed to investigate the variations of hydrogen bond lengths, bond angles, and O-H stretching vibrational frequencies in different substituted systems. The results verify prominent hydrogen bond strengthening in the <i>S</i>₁ state for all derivatives, where substituent electronegativity differences induce distinct excited-state hydrogen bond intensities. Quantum theory of atoms in molecules (QTAIM) topological analysis of bond critical point (BCP) electron density, topological parameters, and hydrogen bond energies confirms that chalcogen electronegativity precisely regulates hydrogen bonding interactions in BPDI systems. Frontier molecular orbitals (FMOs) results show that chalcogen substitution rearranges molecular charge distribution, produces favorable excited-state charge recombination properties, providing suitable electronic structures for ESPT. Potential energy surfaces (PESs) were constructed to elucidate the stepwise ESPT pathways and behavioral differences of the three derivatives. Comparative analysis reveals that solvent polarity effectively modulates excited-state hydrogen bond strength and reaction barriers. Nonpolar solvents notably lower the energy barrier of the first proton transfer step (I → II) and greatly promote ESPT reactions. This work clarifies the dual regulatory mechanism of intrinsic atomic electronegativity and extrinsic solvent polarity effects of BPDI derivatives, offering reliable theoretical guidance for molecular design, performance optimization, and optoelectronic applications of novel BPDI functional materials.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 19","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149145614","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":"The H2 Molecule in Harmonic Cylindrical Potential: Covalent Bond in a Strong Spatial Confinement Regime","authors":"Wojciech Bartkowiak,&nbsp;Mikołaj Marciów,&nbsp;Krzysztof Strasburger","doi":"10.1002/qua.70295","DOIUrl":"https://doi.org/10.1002/qua.70295","url":null,"abstract":"<div>\u0000 \u0000 <p>A detailed study of the influence of the cylindrical harmonic confining potential on the properties of the hydrogen molecule in its ground state is carried out, for the range of angular frequencies of the potential up to 10 a.u. Highly accurate electronic wavefunctions are obtained with the variational method, in the basis of explicitly correlated Gaussian functions. In comparison to the free molecule, the chemical bond of the confined molecule becomes shorter and stronger. Neither the bond length nor the dissociation energy under the strongest considered confinement are influenced considerably by the relativistic effects, although the values of the relativistic energy corrections are large.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 19","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149048147","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":"Exploration of Excited Molecular States With Localized Orbital Locator Function","authors":"Munavvar Husain,&nbsp;Dorota Rutkowska-Zbik,&nbsp;Tatiana Korona","doi":"10.1002/qua.70294","DOIUrl":"https://doi.org/10.1002/qua.70294","url":null,"abstract":"<div>\u0000 \u0000 <p>Localized orbital locator (LOL), which is a function derived from the kinetic energy density, is known to provide detailed features of the electronic structure of molecules in a way close to chemist's viewpoint, that is, by examining and quantifying interatomic connections. In this study we show that the extension of this function to electronic excited states gives an opportunity to explore modifications of the electronic structure caused by electronic excitations. In particular, changes of bond character, number and type of lone pairs, and emergence of long-range features can be detected by the application of LOL to excited-state and ground-state densities. A good agreement between the conclusions from the LOL study and the hole-particle natural transition orbitals (NTO) representation has been found, but the LOL description can be made quantitative and more detailed, if needed. Test calculations supporting these findings have been performed for selected small cases (ethene, tetrafluoroethene, and their dimer) and for the real-life examples of benzaldehyde and 4-pyridin-1-ium-1-ylphenolate.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 19","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149048109","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":"Versatile Adsorption of Oxygenated Volatile Organic Compounds Using Transition-Metal-Decorated Tri-Unit Anthracene-Like hBN","authors":"Salhah D. Al-Qahtani,&nbsp;Mahmoud A. S. Sakr,&nbsp;Ghadah M. Al-Senani,&nbsp;Omar H. Abd-Elkader,&nbsp;Hazem Abdelsalam,&nbsp;Nahed H. Teleb","doi":"10.1002/qua.70298","DOIUrl":"https://doi.org/10.1002/qua.70298","url":null,"abstract":"<div>\u0000 \u0000 <p>Transition-metal single-atom catalysts anchored on two-dimensional nanostructures provide an effective strategy for tuning electronic properties and gas-monitoring behavior. In this work, density functional theory calculations are performed to investigate a tri-unit hexagonal boron nitride framework with an anthracene-like configuration (Tri-hBNA) and its single-atom-decorated derivatives (Ag, Au, Cu Co, Fe, Ni, Pt, and Zn). Structural and binding-energy analyses confirm the high thermodynamic stability of pristine and metal-decorated systems, with metals preferentially anchored at the central region without inducing structural distortion. Metal decoration significantly modulates the wide bandgap of Tri-hBNA by introducing metal-derived states and, for magnetic dopants, spin polarization. Gas-monitoring performance toward methanol and formaldehyde is evaluated via adsorption energies, recovery times, electronic structure, and charge-transfer analyses. Pristine Tri-hBNA shows weak physisorption, whereas metal decoration markedly enhances adsorption. Coinage metals favor reversible detection, while Co, Cu, and Ni induce strong chemisorption, indicating potential for gas capture or activation.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 19","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149048110","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":"Selective Adsorption of Hazardous Gases on C12B8 Nanocages: A Density Functional Theory Investigation","authors":"Shakti S. Ray,&nbsp;Trupti R. Das,&nbsp;Jin Suk Chung,&nbsp;Sung Gu Kang","doi":"10.1002/qua.70297","DOIUrl":"https://doi.org/10.1002/qua.70297","url":null,"abstract":"<div>\u0000 \u0000 <p>This study investigated the potential of a Be-decorated C₁₂B₈ nanocage as a selective and sensitive platform for hazardous gas sensing. Structural optimization identified the C–C bridge as the most favorable binding site for the Be atom, featuring a high binding energy of −3.02 eV. Subsequent adsorption studies involving CH₂, NO₂, NO, NH₃, and H₂Se revealed prominent electronic perturbations, as evidenced by high adsorption energy and substantial charge transfer, which collectively indicated strong adsorbate–substrate interactions. Weaker interactions with CH₄, CO, and SO₂ emphasized the selective adsorption capability of the nanocage. First-principles computations revealed a reduction in hardness and energy gap after the adsorption for reactive gases and confirmed ionic and intermediate bonding characteristics. Additionally, reduced density gradient and density of states analyses validated substantial charge transfer and electronic coupling for reactive gases. These findings establish Be-decorated C₁₂B₈ nanocages as efficient and selective sensors, demonstrating their promising applications in environmental monitoring and industrial safety.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 19","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148994225","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":"A New Half-Projection-Based Treatment for Wave Function Optimization Within the Unrestricted Doubly Occupied Configuration Interaction Framework","authors":"Javier Garcia,&nbsp;Diego R. Alcoba,&nbsp;Luis Lain,&nbsp;Alicia Torre,&nbsp;Gustavo E. Massaccesi,&nbsp;Ofelia B. Oña","doi":"10.1002/qua.70293","DOIUrl":"https://doi.org/10.1002/qua.70293","url":null,"abstract":"<div>\u0000 \u0000 <p>The unrestricted doubly occupied configuration interaction methods have enabled to describe satisfactorily <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>N</mi>\u0000 </mrow>\u0000 <annotation>$$ N $$</annotation>\u0000 </semantics></math>-electron systems, although they very often yield spin-contaminated wave functions. This contamination can partially be reduced by application of the half-projection technique [J. Garcia <i>et al.</i> J. Chem. Phys. <b>161</b>, 224 112 (2024)]. In this work, we propose a new alternative treatment within the half-projection scheme, which leads to results in terms of potential energy curves and their corresponding <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mfenced>\u0000 <msup>\u0000 <mover>\u0000 <mi>S</mi>\u0000 <mo>^</mo>\u0000 </mover>\u0000 <mn>2</mn>\u0000 </msup>\u0000 </mfenced>\u0000 </mrow>\u0000 <annotation>$$ leftlangle {hat{S}}^2rightrangle $$</annotation>\u0000 </semantics></math> expectation values in prototype strongly correlated <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>N</mi>\u0000 </mrow>\u0000 <annotation>$$ N $$</annotation>\u0000 </semantics></math>-electron systems. These results have been systematically compared with those obtained from previously reported treatments using half-projection techniques, with those of the ordinary unrestricted doubly occupied configuration interaction procedure, and with those arising from the full configuration interaction method. We show that the new proposed method allows for a further reduction in the spin contamination, while it does not require significant increases in computational costs.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 19","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148994265","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":"Tailoring Mechanical Stability and Electronic Structure in TiNiSn-Based Half-Heusler Alloys via Sn-Site Doping: A DFT Study","authors":"Md. Rafedul Haque,&nbsp;Md. Ali Munna,&nbsp;Sanjida Ahmed Saima,&nbsp;Zahid Hasan","doi":"10.1002/qua.70296","DOIUrl":"https://doi.org/10.1002/qua.70296","url":null,"abstract":"<div>\u0000 \u0000 <p>Half-Heusler compounds are promising quantum materials for thermoelectric applications due to their excellent electronic properties, including semiconductivity, thermoelectricity and topological insulating behavior. However, optimizing their mechanical stability and optical phenomena remains a challenge. This study employs density functional theory (DFT) with the generalized gradient approximation (GGA-PBE) for the exchange-correlation functional to characterize the novel quaternary Half-Heusler alloys ANiSn_0.5M_0.5 (A = Zr, Ti; M = Si, Ge, Sb). The structural, electronic, thermodynamic, mechanical and optical properties were systematically analyzed. Although the compositions via fractional substitution are unexplored, this investigation reported a comparison analysis alongside prior articles on related samples. Surprisingly, structural analysis suggests that the samples exhibit a cubic to tetragonal transition, while elastic constants confirm that TiNiSn_0.5Si_0.5 and TiNiSn_0.5Sb_0.5 are highly mechanically stable materials. Moreover, Pugh's ratio of 2.01 (for TiNiSn_0.5Si_0.5) and 3.25 (for TiNiSn_0.5Sb_0.5), alongside Debye temperatures of 360.02 and 231.43 K, respectively, were obtained, indicating a ductile character and strong phonon scattering and potentially low lattice thermal conductivity. Electronic structure analysis shows that Sb doping introduces metallic behavior, while Si/Ge alloying maintains semiconducting character. Furthermore, optical behavior reveals higher absorption at the visible-lower UV regions, fluctuated reflectivity around 0.5 and a lower level of conductivity and dielectric constant. While fractional Sn-site substitution strategies have precedent in related half-Heusler families, the specific ANiSn_0.5M_0.5 compositions examined here, together with their combined electronic, mechanical, and optical characterization, have not been previously reported, and this investigation situates the results within the context of prior work on related compounds.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 19","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148994264","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":"Field-Assisted Substrate Ionization as a Plausible Initiating Step in Enzyme Catalysis","authors":"Marianne Kerleaux,&nbsp;Florian Regnier,&nbsp;Jean-Nicolas Vigneau,&nbsp;Chérif F. Matta","doi":"10.1002/qua.70283","DOIUrl":"https://doi.org/10.1002/qua.70283","url":null,"abstract":"<p>Enzymes are widely understood to accelerate chemical reactions through transition-state stabilization and optimizing the orientation of reactants within their active sites. A growing body of work highlights the central role of strong electrostatic fields in these processes with magnitudes reaching ∼10⁸–10¹⁰ V/m in enzyme active sites. Here, we explore the hypothesis that such fields may, in some cases, facilitate catalysis by inducing field-assisted electron transfer or partial ionization of bound substrates. To assess the plausibility of this mechanism, a semiclassical tunneling expression in the quasistatic limit was applied to two datasets of enzymatic substrates: a curated set of 54 substrates with experimentally known ionization potentials and an extended set of 3168 enzymatic substrates with machine-learning-predicted ionization potentials matched to 5272 enzymes. At field strengths of an order ≳ 10¹⁰ V/m, estimated ionization rates span the nanosecond-to-picosecond regime for a subset of substrates, suggesting that field-induced tunneling may render electron-transfer events statistically accessible within the residence time of enzyme–substrate complexes. These results are recast in probabilistic terms, showing that even modest tunneling rates can lead, under certain circumstances, to non-negligible ionization probabilities over biologically relevant timescales. Electronic-structure calculations on the ketosteroid isomerase substrate (5-androstene-3,17-dione) indicate that one-electron oxidation leads to a redistribution of electron density consistent with the enhancing of the electrophilic character of the molecule's reactive site. While the tunneling expressions employed here are not intended to provide quantitatively predictive rates in condensed enzymatic environments, they offer a physically motivated metric for assessing the sensitivity of ionization barriers to strong electrostatic fields. Taken together, these results suggest that field-assisted substrate ionization or oxidation may represent a plausible, though not yet established, mechanistic component in certain enzyme-catalyzed reactions. This hypothesis remains qualitative and is intended to stimulate further theoretical and experimental testing.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 19","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70283","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148965548","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}