International Journal of Quantum Chemistry最新文献

{"title":"|∆μ| Big Is “Not Bad”? A Quantitative Assessment","authors":"Abdul Rahman Al Nabulsi,&nbsp;Farnaz Heidar-Zadeh,&nbsp;Ramón Alain Miranda-Quintana,&nbsp;Paul W. Ayers","doi":"10.1002/qua.70258","DOIUrl":"https://doi.org/10.1002/qua.70258","url":null,"abstract":"<p>We perform a thorough test of the “<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mo>|</mo>\u0000 <mi>Δ</mi>\u0000 <mi>μ</mi>\u0000 <mo>|</mo>\u0000 </mrow>\u0000 <annotation>$$ mid Delta mu mid $$</annotation>\u0000 </semantics></math> big is good” principle (DMB) using double-exchange reactions between diatomic molecules. We conclude that DMB is “not bad” at predicting whether or not a reaction will be favorable, but its performance is inferior to alternatives like the maximum hardness principle.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 13","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70258","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148386347","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":"Fubini-Study Metric Tensor Evolution and Reduced State Distinguishability in Geometry-Aware Optimization for Reliable Near-Term Variational Quantum Eigensolvers","authors":"Dwi Cahyo Mariyanto,&nbsp;Hadyan L. Prihadi,&nbsp;Angga Dito Fauzi,&nbsp;L. T. Handoko,&nbsp;Yanoar P. Sarwono,&nbsp;Rui-Qin Zhang","doi":"10.1002/qua.70255","DOIUrl":"https://doi.org/10.1002/qua.70255","url":null,"abstract":"<p>The lack of both a consistently effective and broadly reliable classical optimizer for variational quantum algorithms and a clear physical understanding of how the Fubini-Study (FS) metric evolves during optimization remains a central challenge for practical variational quantum eigensolver (VQE) applications. In this work, we systematically investigate the quantum natural gradient (QNG) as a geometry-aware optimization strategy and benchmark its performance against commonly used classical optimizers, including gradient-based, derivative-free, and adaptive methods. Using representative molecular systems, we analyze energy convergence, parameter-space trajectories, and the dynamical evolution of the FS metric tensor. QNG consistently achieves faster and more stable convergence in the studied molecules by aligning parameter updates with the intrinsic curvature of the quantum state manifold. The evolution of the metric reveals a rapid suppression of irrelevant parameter directions and a reduced state distinguishability near the ground state. Obtained under ideal and simplified noise conditions, these results clarify the geometric origin of QNG advantage and highlight the potential suitability of geometry-aware optimization for robust VQE implementation on near-term quantum devices.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 13","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70255","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148386960","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":"Ab Initio Investigation of MgXe, Its Cation Mg+Xe and Clusters Mg+Xen: Electronic Structure, Spectroscopic Properties, and Temperature-Dependent Absorption Spectra","authors":"M. Bejaoui,&nbsp;S. Awali,&nbsp;W. Zrafi,&nbsp;J. Dhiflaoui,&nbsp;H. Berriche","doi":"10.1002/qua.70252","DOIUrl":"https://doi.org/10.1002/qua.70252","url":null,"abstract":"<p>One and two electron pseudopotential approaches were employed to investigate the electronic and spectroscopic properties of the Mg⁺Xe and MgXe van der Waals complexes. In this study, potential energy curves (PECs) were computed at the SCF level for the Mg⁺Xe system, whereas both SCF and full configuration interaction (FCI) calculations were performed for the neutral MgXe complex. In addition, the core–core interaction, denoted as Mg²⁺Xe, was treated using the CCSD(T) method. Furthermore, spin–orbit coupling effects were explicitly included for the first excited B²Σ⁺ and A²Π electronic states. Spectroscopic parameters obtained for the ground and low-lying excited states are compared with existing experimental and theoretical results, showing good agreement and contributing to a deeper understanding of the interaction between Mg and Xe in various electronic states. The temperature dependence of the absorption spectrum of a Mg atom adsorbed on Xe_<i>n</i> (<i>n</i> = 1–7) clusters is also investigated using a combined Monte Carlo (MC) method with basin hopping global optimization to simulate the geometries of the xenon clusters in the 3s–3p transition at temperature T. Transition dipole moments are also calculated for the X²Σ⁺ → A²Π₁/₂, ₃/₂ and X²Σ⁺ → B²Σ⁺₁/₂ transitions.</p>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 13","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70252","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148387030","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":"Modeling of Ba2SrCrO6 Double Perovskite Oxide for Solar Cells With High Energy Conversion Efficiency Using DFT and SCAPS-1D Simulation","authors":"Ayoub Boufoud,&nbsp;Kamal Elasri,&nbsp;EL Mokhtar Darkaoui,&nbsp;Fouad Agoujil,&nbsp;Sabrine El Asri,&nbsp;Mohamed Karouchi,&nbsp;Said Mouslih,&nbsp;Abderrahman Abbassi,&nbsp;Soukaina Ed-Dahri,&nbsp;Souad Taj,&nbsp;Mohamed Hssikou,&nbsp;Bouzid Manaut,&nbsp;Atika Fahmi","doi":"10.1002/qua.70259","DOIUrl":"https://doi.org/10.1002/qua.70259","url":null,"abstract":"<div>\u0000 \u0000 <p>In this study, the structural, electronic, optical, thermoelectric, and photovoltaic properties of Ba₂SrCrO₆ were investigated in order to evaluate its potential for photovoltaic applications. The results reveal that this material exhibits remarkable stability in its various forms, namely structural, mechanical, thermodynamic, and dynamic stability, along with attractive properties, manifesting as a semiconductor behavior with a narrow indirect band gap of 1.005 eV. Furthermore, a high optical absorption coefficient in the visible region, reaching <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mn>4</mn>\u0000 <mo>×</mo>\u0000 <msup>\u0000 <mn>10</mn>\u0000 <mn>5</mn>\u0000 </msup>\u0000 </mrow>\u0000 <annotation>$$ 4times {10}^5 $$</annotation>\u0000 </semantics></math> cm⁻¹, highlights its strong ability to harvest solar light. To further evaluate its device-level performance, the photovoltaic behavior of Ba₂SrCrO₆ was studied using SCAPS-1D simulations. The optimization of the solar cell architecture FTO/ZnO/Ba₂SrCrO₆/CBTS/Au, achieved by tuning the absorber layer thickness, operating temperature, and selecting appropriate electron and hole transport layers, significantly improved the device performance. The optimized structure exhibits a power conversion efficiency (PCE) of 26.89%, with a fill factor of 86.3%, a short-circuit current density of 28.04 mA/cm², and an open-circuit voltage of 1.24 V at room temperature, demonstrating the strong potential of Ba₂SrCrO₆ as an absorber material for high-efficiency solar cells.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 13","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148386961","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":"Compounds With Allene Moiety as a Component in the [3+2] Cycloaddition Reactions: A Molecular Electron Density Theory Study","authors":"Nikola Samborek,&nbsp;Olaf Kukulski,&nbsp;Agnieszka Kącka-Zych","doi":"10.1002/qua.70256","DOIUrl":"https://doi.org/10.1002/qua.70256","url":null,"abstract":"<div>\u0000 \u0000 <p>The [3+2] cycloaddition (32CA) reactions involving C-phenyl-N-methylnitrone and (phenylsulfonyl)propadiene have been theoretically studied within the molecular electron density theory (MEDT). Topological analysis of the electron localization function (ELF) of the reagents allowed us to learn the electronic structure of the mentioned reagents. Analysis of conceptual density functional theory (CDFT) indices indicates that the nitrone will play the role of a strong nucleophile, while (phenylsulfonyl)propadiene will act as a strong electrophile. According to the local Parr functions of the reagents, the most favorable reaction path of these 32CA reactions will be initialized by the nucleophilic attack of the O3 of nitrone on the central electrophilic C4 carbon of the (phenylsulfonyl)propadiene. In the study reaction, we noticed two theoretically possible reaction paths (A and B) leading to two stereoisomeric products. The Gibbs free energy for Path A of the 32CA reaction is higher than that for Path B of the 32CA reaction, and according to that, Path A should be considered kinetically unfavored. A bonding evolution theory (BET) study of the more favorable channel B associated with the 32CA reaction indicates that this reaction is associated with a highly asynchronous <i>one-step</i>, <i>two-stage</i> mechanism in which the activation energy is related to the formation of a <i>pseudoradical</i> center at the C4 carbon atom and V(N2) monosynaptic basin.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 13","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148386925","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 Comparative Analysis of Molecular Interactions and Ion Transport Between Dextrose and L-Tyrosine in Ethaline-DES for Li-Ion Batteries","authors":"Akshay Sharma,&nbsp;Renuka Sharma,&nbsp;Ramesh Chand Thakur","doi":"10.1002/qua.70250","DOIUrl":"https://doi.org/10.1002/qua.70250","url":null,"abstract":"<div>\u0000 \u0000 <p>Deep eutectic solvents (DESs) are emerging as sustainable electrolytes for Li-ion batteries, yet their performance is fundamentally governed by complex molecular interactions. In this work, we present a comparative study of two bio-additives, dextrose and L-tyrosine, in ethaline-DES to understand their influence on transport properties. Experimental density, viscosity, and ionic conductivity measurements, supported by Walden analysis, revealed that L-tyrosine induces a significant positive deviation from ideality, indicating enhanced ion dissociation compared to dextrose. Computational modeling provided a molecular-level explanation for these observations. DFT calculations demonstrated that the formation of Lithium salt-additive complexes is thermodynamically spontaneous and stabilized by strong hydrogen bonding. Crucially, Molecular Dynamics (MD) simulations establish that L-tyrosine forms a significantly more compact and rigid primary solvation shell around the Li cation compared to the broader coordination of dextrose. This targeted, rigid steric shielding effectively isolates the lithium cation from the perchlorate anion, suppressing ion-pairing and improving the lithium transport number. By correlating macroscopic transport properties with molecular-level insights, this work establishes L-tyrosine as a superior additive for designing safer and more efficient DES-based electrolytes.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 13","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148386924","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":"Computational Investigation of Hydrogen Storage and Photocatalytic Potential of Double-Hydride Perovskites Rb2LiXH6 (X = Al, B)","authors":"I. Zeba,&nbsp;S. S. A. Gillani,&nbsp;Rabia Aslam,&nbsp;Maira Mureed,&nbsp;Safa Arshad,&nbsp;Daud Akhtar","doi":"10.1002/qua.70248","DOIUrl":"https://doi.org/10.1002/qua.70248","url":null,"abstract":"<div>\u0000 \u0000 <p>In this study, we have investigated the structural and physical properties of Rb₂LiXH₆ (where X = Al, B) by using density functional theory, with particular focus on its photocatalytic, optoelectronic, phonon, and thermodynamic features, highlighting its potential for hydrogen storage applications. The results reveal that both substances, Rb₂LiAlH₆ and Rb₂LiBH₆, exhibit a cubic crystal structure, with computed lattice parameters of 5.98 and 5.74 Å, respectively. Moreover, the calculations of formation and cohesive energies for the studied structures confirm that both materials are feasible to synthesize and exhibit thermodynamic stability. Hydrogen storage properties, including gravimetric and volumetric capacities and desorption temperatures, are evaluated. The gravimetric capacities are reported as 2.86% for Rb₂LiAlH₆ and 3.11% for Rb₂LiBH₆. In this research, the \u0000photocatalytic activity was also assessed, indicating that the Rb₂LiAlH₆ compound exhibits improved photocatalytic performance, supporting its suitability for photocatalytic water splitting. The electronic band structure shows that Rb₂LiAlH₆ and Rb₂LiBH₆ compounds exhibit indirect band-gap semiconducting behavior, with GGA band gaps of 1.809 and 0.096 eV and HSE-03 band gaps of 2.603 and 0.383 eV, respectively. Both double perovskite hydrides exhibit \u0000mechanical stability and demonstrate brittle properties, as revealed by Poisson's and Pugh's ratios. Thermodynamic parameters, including \u0000heat capacity, enthalpy, entropy, \u0000Debye temperature, melting temperature, lattice parameters, and minimum thermal conductivity, are analyzed to assess stability at elevated temperatures and suitability for industrial applications. The \u0000optical properties indicate that Rb₂LiAlH₆ and Rb₂LiBH₆ exhibit enhanced absorption coefficients in the order of (10⁴ cm⁻¹) and hold potential for \u0000optoelectronic applications in the UV and visible regions. The overall analysis reveals Rb₂LiXH₆ (where X = Al, B) as a promising applicant for future H₂ retention due to its favorable gravimetric capacity and remarkable resilience.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 13","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148324522","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 Study on the Impact of Beryllium Doping on the Structural and Electronic Characteristics of Anionic Boron Clusters","authors":"Zhi Wei Tan,&nbsp;Yan Fei Hu,&nbsp;De Hui Zhou,&nbsp;Guo Liang Xiang,&nbsp;Miao Dan Wei,&nbsp;Han Zhe Qin,&nbsp;Zi Meng Dong","doi":"10.1002/qua.70253","DOIUrl":"https://doi.org/10.1002/qua.70253","url":null,"abstract":"<div>\u0000 \u0000 <p>This study employs the CALYPSO structure prediction approach integrated with particle swarm optimization (PSO) as the principal methodological framework, in conjunction with DFT calculations, to perform a comprehensive global search and precise identification of the ground-state and metastable configurations of Be₂B_<i>n</i>⁻ (<i>n</i> = 1–12) anionic boron clusters. Initial structural candidates were systematically generated and finally optimized at the M06L/def2svp computational level. Structures were evaluated by comparing total energies and point group symmetries to identify metastable configurations and ground states. Be doping significantly alters the geometry of B clusters, with the double pyramidal D_7H Be₂B₇⁻ cluster showing the highest stability. Spectral analysis provided a more comprehensive insight into the properties of Be₂B_<i>n</i>⁻ (<i>n</i> = 1–12) clusters. Moreover, bonding studies revealed <i>s–p</i> hybridization between the 2<i>s</i> and 2<i>p</i> AOs of B and 2<i>p</i> AOs of Be in Be₂B₇⁻. Adaptive natural density partitioning (AdNDP) and aromaticity assessments confirmed significant <i>π</i> aromaticity in this cluster. Electrostatic potential (ESP) analysis indicated that B–B bonds are prone to interactions with positively charged entities.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"126 13","pages":""},"PeriodicalIF":2.7,"publicationDate":"2026-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148324401","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 50-Year Historical Perspective of the Extended Koopmans' Theorem, Its Exactness, and Future Prospects","authors":"Robert C. Morrison","doi":"10.1002/qua.70247","DOIUrl":"https://doi.org/10.1002/qua.70247","url":null,"abstract":"<p>The early history of the extended Koopmans' theorem is reviewed. Two research groups independently developed the extended Koopmans' theorem to calculate ionization energies from density matrices. Initially it was implemented for full configuration interaction and multi-configurational self-consistent field wave functions. Later it was implemented using other optimization methods. The long history of studies of the exactness of the extended Koopmans' theorem for ionization is discussed, as well as limits of accuracy for electron affinities. Its utility in obtaining Dyson orbitals for application in studies of chemical reactivity, for which orbital models have been instrumental to our understanding of chemical reactions, is discussed.</p>","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":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/qua.70247","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148274718","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":"Pair Density Shannon Information Measures and Their \u0000 \u0000 \u0000 N\u0000 \u0000 $$ N $$\u0000 -Dependent Behavior in Diatomic Molecular Systems","authors":"Saúl J. C. Salazar,&nbsp;J. Antonio Zárate,&nbsp;J. M. Solano-Altamirano,&nbsp;Humberto G. Laguna,&nbsp;Julio M. Hernández-Pérez,&nbsp;Robin P. Sagar","doi":"10.1002/qua.70246","DOIUrl":"https://doi.org/10.1002/qua.70246","url":null,"abstract":"<div>\u0000 \u0000 <p>Pair density Shannon entropies and mutual information in position and in momentum space are calculated for two series of homonuclear and heteronuclear diatomic molecules using Hartree–Fock wave functions. The pair density entropy sum increases with the quality of the basis set. Mutual information, a measure of statistical correlation, is seen to be smaller in momentum space as compared to position space. The interpretation is that the momentum pair density is closer than the position pair density to a Hartree-like reference. The <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>N</mi>\u0000 </mrow>\u0000 <annotation>$$ N $$</annotation>\u0000 </semantics></math>-dependent behaviors of the entropy and mutual information sums are examined by fitting the data to three different model behaviors. Results show that these models are capable of representing the molecular data in differing degrees. The parameters obtained from a particular model are relatively constant across different chemical series. This adds evidence to the argument of a universal <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>N</mi>\u0000 </mrow>\u0000 <annotation>$$ N $$</annotation>\u0000 </semantics></math>-dependent behavior of the entropy sums.</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":"148282430","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}