International Journal of Quantum Chemistry最新文献

{"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}

{"title":"Tunable Electronic and Optical Properties of LiN1−xPxMg Half-Heusler Phases for Advanced Optoelectronic Applications","authors":"Iqra Qasim,&nbsp;Beriham Basha,&nbsp;Farah Andleeb,&nbsp;Talal M. Althagafi,&nbsp;M. S. Al-Buriahi,&nbsp;Memoona Mehmood,&nbsp;Muhammad Nasir Rasul","doi":"10.1002/qua.70281","DOIUrl":"https://doi.org/10.1002/qua.70281","url":null,"abstract":"<div>\u0000 \u0000 <p>The structural, electronic, bonding, and optical properties of LiN_1−<i>x</i>P_<i>x</i>Mg (<i>x</i> = 0, 0.25, 0.5, 0.75, and 1) half-Heusler alloys were investigated using density functional theory within the GGA and modified Becke–Johnson (mBJ) frameworks. Attention was given to the intermediate compositions (<i>x</i> = 0.25, 0.5, and 0.75), for which detailed theoretical data are not available in the literature. Structural optimization confirms the stability of all investigated compositions and shows that phosphorus substitution leads to a nonlinear expansion of the lattice together with a gradual reduction in stiffness. Among the studied alloys, the <i>x</i> = 0.5 composition exhibits the lowest equilibrium energy, indicating enhanced energetic stability. Electronic structure calculations reveal a clear composition-dependent evolution of the band gap, with direct-gap semiconducting behavior preserved up to <i>x</i> = 0.75 and a transition to an indirect band gap in LiPMg (<i>x</i> = 1). The mBJ calculations predict tunable band gaps ranging from 3.48 to 1.74 eV, highlighting the strong influence of alloying on the electronic properties. Bonding analyses based on COHP, charge transfer, and electron localization function calculations further show that replacing N with P modifies the bonding environment and promotes changes in electron distribution across the lattice. In addition, all compositions exhibit strong optical activity in the visible and ultraviolet regions, characterized by enhanced absorption, optical conductivity, and inter band transitions. These results demonstrate that phosphorus substitution offers an effective route for tailoring the electronic and optical response of LiN_1−<i>x</i>P_<i>x</i>Mg alloys, making them promising candidates for future optoelectronic and photonic applications.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 18","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148942852","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":"Intensive Static Quantum Chemistry and AIMD Theoretical Investigations of Molecular Stacking and Charge-Transfer Mechanisms in PM6:PY-X Organic Solar Cells","authors":"Abdelghani Adda,&nbsp;Roquiya Nour El Houda Zorgani,&nbsp;Mohammed Aymen Zorgani,&nbsp;Abdelmalik Seddiki,&nbsp;Abbes Djelaili,&nbsp;Moussa Sehailia,&nbsp;Abdelghani Mohamed Krallafa","doi":"10.1002/qua.70292","DOIUrl":"https://doi.org/10.1002/qua.70292","url":null,"abstract":"<div>\u0000 \u0000 <p>Organic solar cells based on donor–acceptor heterojunctions rely on interfacial charge transfer (CT) for exciton dissociation and charge transport. This study combines DFT, TD-DFT, and AIMD simulations to investigate the electronic structure and CT properties of PM6 donor dimers with PY-X non-fullerene acceptors (X = CH₃, OCH₃, CN, COCH₃, NH₂, NHCH₃), using PM6:PY-CH₃ as the reference. Three substituted derivatives are highlighted: PY-CN and PY-COCH₃ exhibit strong CT character (∼54%–51%), low band gaps (∼2.0 eV), and deep LUMO levels favoring electron transfer, while PY-NHCH₃ offers a high open-circuit voltage (1.76 eV) and fill factor (92%) despite weak CT (∼6.6%). Notably, after AIMD simulations in explicit chloroform, the most optically active excited state of the PM6:PY-CN dimer exhibits a high CT character (∼56.56%), together with the smallest band gap indicating highly efficient exciton dissociation. AIMD simulations in chloroform reveal that solvent-induced structural relaxation enhances CT interactions and stabilizes the donor–acceptor interface. Overall, substituent effects, solvent interfacial interactions, and π–π stacking are key modulators of exciton dissociation and charge transport, offering design guidelines for high-performance, stable organic solar cells.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 18","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148942853","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":"Substituent-Driven Modulation of Electronic Properties in Acrylonitrile Derivatives: A Combined Study on NLO Response and DNA-Binding Affinity via ECT Analysis","authors":"Furkan Özen,&nbsp;Bayram Gündüz,&nbsp;Günseli Turgut Cin,&nbsp;Leyla Babali Özen,&nbsp;Öner Ekici","doi":"10.1002/qua.70289","DOIUrl":"https://doi.org/10.1002/qua.70289","url":null,"abstract":"&lt;p&gt;This study presents a systematic investigation into the substituent-driven modulation of the electronic, optical, and biological properties of two &lt;i&gt;methoxy&lt;/i&gt;-substituted acrylonitrile derivatives, denoted as &lt;b&gt;C-1&lt;/b&gt; (&lt;i&gt;m&lt;/i&gt;-CF&lt;sub&gt;3&lt;/sub&gt; substituted) and &lt;b&gt;C-2&lt;/b&gt; (&lt;i&gt;p&lt;/i&gt;-CH&lt;sub&gt;3&lt;/sub&gt; substituted). While experimental data revealed a striking parity in their optical band gaps (&lt;i&gt;E&lt;/i&gt;&lt;sub&gt;g&lt;/sub&gt; = 3.3 eV in DMSO), their distinct electronic profiles prompted a deeper theoretical probe to differentiate their microscopic performances. Density Functional Theory (DFT) calculations at the B3LYP/6–311++G(d,p) level for ground-state properties and B3LYP/6–311G(d,p) for TD-DFT calculations were employed to elucidate the underlying electronic mechanisms. Natural Bond Orbital (NBO) analysis demonstrated that both systems exhibit efficient intramolecular charge transfer (ICT) across the acrylonitrile bridge. Furthermore, range-separated hybrid DFT calculations (CAM-B3LYP/6–311++G(d,p)) were performed to accurately evaluate the non-linear optical (NLO) responses without global hybrid overpolarization artifacts. The calculations revealed comparable, robust first-order hyperpolarizabilities (&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;msub&gt;\u0000 &lt;mi&gt;β&lt;/mi&gt;\u0000 &lt;mi&gt;tot&lt;/mi&gt;\u0000 &lt;/msub&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ {beta}_{mathrm{tot}} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt;) for both derivatives (&lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;1.48&lt;/mn&gt;\u0000 &lt;mo&gt;×&lt;/mo&gt;\u0000 &lt;msup&gt;\u0000 &lt;mn&gt;10&lt;/mn&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;mn&gt;29&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msup&gt;\u0000 &lt;mspace&gt;&lt;/mspace&gt;\u0000 &lt;mi&gt;esu&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ 1.48times {10}^{-29} mathrm{esu} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; for &lt;b&gt;C-1&lt;/b&gt; and &lt;span&gt;&lt;/span&gt;&lt;math&gt;\u0000 &lt;semantics&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mn&gt;1.30&lt;/mn&gt;\u0000 &lt;mo&gt;×&lt;/mo&gt;\u0000 &lt;msup&gt;\u0000 &lt;mn&gt;10&lt;/mn&gt;\u0000 &lt;mrow&gt;\u0000 &lt;mo&gt;−&lt;/mo&gt;\u0000 &lt;mn&gt;29&lt;/mn&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;/msup&gt;\u0000 &lt;mspace&gt;&lt;/mspace&gt;\u0000 &lt;mi&gt;esu&lt;/mi&gt;\u0000 &lt;/mrow&gt;\u0000 &lt;annotation&gt;$$ 1.30times {10}^{-29} mathrm{esu} $$&lt;/annotation&gt;\u0000 &lt;/semantics&gt;&lt;/math&gt; for &lt;b&gt;C-2&lt;/b&gt; in DMSO), significantly exceeding the benchmark urea threshold. To explore the theoretical quantum-chemical reactivity profiles of these chromophores, Electrophilicity Charge Transfer (ECT) analysis was utilized to model","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 18","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70289","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148903967","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":"D-Carbazole-A Compounds: Modulation of Second-Order Nonlinear Optical Properties by Substituent Types and Positional Isomerism","authors":"Jin-Zhe Zhang,&nbsp;Sarula Jin,&nbsp;Feng-Yang Bai,&nbsp;Li-Hui Wang,&nbsp;Jin-Ting Ye","doi":"10.1002/qua.70291","DOIUrl":"https://doi.org/10.1002/qua.70291","url":null,"abstract":"<div>\u0000 \u0000 <p>Three-dimensional materials exhibiting through-space charge transfer (TSCT) have garnered extensive research interest in the field of nonlinear optics (NLO). In this work, density functional theory (DFT) was employed to systematically investigate a series of donor (D)-carbazole-acceptor (A) type compounds (<b>1–6</b>) and traditional D–A type compounds <b>7</b> and <b>8</b>. Their geometric structures, absorption spectra, charge transfer characteristics, and second-order NLO properties were analyzed, with emphasis on clarifying the influences of D/A types and substitution positions on the first hyperpolarizability (<i>β</i>_tot) and charge transfer (CT) processes. The results reveal that replacing the acceptor unit from phthalimide (compound <b>6</b>) to dibenzo[a,c]phenazine (compound <b>3</b>) results in a 3.86-fold enhancement in the <i>β</i>_tot value, whereas variations in the donor moiety or substitution position exert relatively weaker effects. This demonstrates that the D-carbazole-A skeleton is highly sensitive to acceptor modifications and plays a dominant role in modulating the second-order NLO properties. Notably, the <i>β</i>_tot value of compound <b>6</b> (2.2 × 10⁻³⁰ esu) is significantly lower, which can be attributed to its unique orbital contributions (HOMO → LUMO + 1), distinct TSCT character, and smaller oscillator strength of the main excited state. In summary, the types and positions of substituents and the CT mode can effectively modulate the second-order NLO response, providing new strategies for the design of novel NLO materials.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 18","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148903966","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":"Isopropenylation of Methanol in KOH·0.5H2O/NMP and KOH/DMSO Superbasic Media: A Comparative Quantum Chemical Study of the Reaction Mechanism","authors":"Yuliya A. Orlyuk,&nbsp;Alexander S. Bobkov,&nbsp;Nikita V. Teplyashin,&nbsp;Nadezhda M. Vitkovskaya","doi":"10.1002/qua.70290","DOIUrl":"https://doi.org/10.1002/qua.70290","url":null,"abstract":"<div>\u0000 \u0000 <p>The influence of the superbase nature on the reaction mechanism of the methanol isopropenylation with a propyne-allene mixture in the KOH·0.5H₂O/NMP and KOH/DMSO systems has been studied using a combined quantum chemical approach including DFT methods (B2PLYP-D2/6–311+G**//B3LYP/6–31+G* + PCM). The superbases are modeled by the pentasolvate complexes KOH·5NMP, KOH·H₂O·5NMP and KOH·5DMSO. According to the results obtained, the reaction proceeds preferentially via the addition of methoxide ion to allene, and this is the rate-determining stage. A significant decrease in the yield of the reaction product in the KOH·0.5H₂O/NMP system (KOH·H₂O·5NMP complex) compared to KOH/DMSO (KOH·5DMSO complex) is explained by a higher activation barrier associated with the hydration of the attacking nucleophile. The lower activation barrier of the rate-determining stage obtained in the presence of KOH·5NMP, compared to KOH·5DMSO, shows the competitiveness of the KOH/NMP system over KOH/DMSO in the vinylation of alcohols by propyne-allene mixture under anhydrous conditions.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 18","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148903948","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 “Can B3LYP Be Improved by Optimization of the Proportions of Exchange and Correlation Functionals?”","authors":"","doi":"10.1002/qua.70280","DOIUrl":"https://doi.org/10.1002/qua.70280","url":null,"abstract":"<p>\u0000 <span>L. Lu</span>, “ <span>Can B3LYP be Improved by Optimization of the Proportions of Exchange and Correlation Functionals?</span>,” <i>International Journal of Quantum Chemistry</i> <span>115</span> (<span>2015</span>): <span>502</span>–<span>509</span>, https://doi.org/10.1002/QUA.24876.</p><p>An improved version of B3LYP obtained by refining empirical parameters in B3LYP functional against accurate experimental, which was denoted as OpB3LYP in this article, is the same functional reported as revB3LYP in the “An improved B3LYP method in the calculation of organic thermochemistry and reactivity” published on <i>Computational and Theoretical Chemistry</i> in volume 1015 (2013), 64–71. In this article, we have presented more details on parameter optimization and more extensive tests on the general good performance of revB3LYP. Unfortunately, the previous CTC paper has not been cited correctly in IJQC paper. To correct this oversight, we add the erratum to this article, and a statement should be added in the introduction section in our IJQC paper as follows:</p><p>In this work, empirical parameters in B3LYP functional, <i>a</i>₀, <i>a</i>_X, and <i>a</i>_C, are refined against accurate experimental data, the detailed procedure that we have performed to improve B3LYP functional is presented, and the performance of a better version of B3LYP denoted as OpB3LYP, which is identical to the revB3LYP functional in the previous work [R1], has been systematically characterized and statistically analyzed.</p><p>[R1] L. Lu, H. Hu, H. Hou, B. Wang, <i>Computational and Theoretical Chemistry</i> 1015 (2013): 64.</p><p>B3LYP is the most widely used hybrid DFT functional. The relative weight of each component in B3LYP is determined by three empirical parameters. A global optimization of these parameters against accurate experimental reference is performed to obtain an improved version of the functional called OpB3LYP. OpB3LYP significantly improves the accuracy and overcomes the size dependence problems of B3LYP.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 17","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70280","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148942404","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":"Strain-Mediated Electronic Structure Reconstruction of Frenkel Defects in Monolayer MoSe2: A First-Principles Study","authors":"Xinyi Lu,&nbsp;Jinying Li,&nbsp;Li Wang,&nbsp;Chunwei Yang","doi":"10.1002/qua.70288","DOIUrl":"https://doi.org/10.1002/qua.70288","url":null,"abstract":"<div>\u0000 \u0000 <p>Using first-principles DFT, we investigate the synergistic modulation of the electronic structure of monolayer MoSe₂ by biaxial strain and Frenkel defects for electrocatalytic hydrogen evolution. A biaxial compressive strain of −4% lowers the Frenkel defect formation energy from 2.41 eV to 1.85 eV. The defect-strain synergy introduces in-gap states, increases the density of states at the Fermi level, modulates the Mo d-band center, strengthens orbital hybridization, and optimizes surface charge distribution and work function. Consequently, the hydrogen adsorption free energy (ΔG_H*) changes from 1.92 eV on the pristine basal plane to −0.01 eV, approaching the ideal thermodynamic value. Detailed analysis of the correlation between the <i>d</i>-band center and ΔG_H* elucidates the microscopic origin of this optimization. Phonon dispersion and AIMD simulations confirm dynamical stability at room temperature. This work reveals the microscopic mechanism of strain–defect coupling in enhancing catalytic activity and provides a physical basis for the rational design of two-dimensional transition metal dichalcogenide electrocatalysts for clean energy applications.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 17","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148942158","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}