International Journal of Quantum Chemistry最新文献

{"title":"Comparative Analysis of Kekulene Tessellation Patterns Using Generalized Reverse Degree-Sum Descriptors Combined With Graph Entropy and Energy Properties","authors":"AR. Abul Kalaam,&nbsp;A. Berin Greeni","doi":"10.1002/qua.70043","DOIUrl":"https://doi.org/10.1002/qua.70043","url":null,"abstract":"<div>\u0000 \u0000 <p>Molecular descriptors are essential tools for analyzing the structural and physicochemical properties of molecular systems. In this study, novel modified reverse degree-sum descriptors are applied to analyze kekulenes, a distinctive class of cycloarenes known for their aromaticity, superaromaticity, and exceptional electronic properties. These descriptors are further integrated with graph entropy measures to evaluate the structural complexity and energetic properties of three kekulene tessellation patterns: Zigzag, armchair, and rectangular. Energetic parameters, including total <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>π</mi>\u0000 </mrow>\u0000 <annotation>$$ pi $$</annotation>\u0000 </semantics></math>-electron energy, HOMO-LUMO energy gaps, and resonance energy, are computed to provide a detailed understanding of the kinetic and thermodynamic stability of these tessellations. The modified reverse degree-sum-based methodology applies to all degree-sum-based descriptors. The variable parameter ‘<span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mi>k</mi>\u0000 </mrow>\u0000 <annotation>$$ k $$</annotation>\u0000 </semantics></math>’ adjusts the molecular graph's degree-sum sequence to best fit the unique properties of each dataset. These enhancements strengthen correlations with physicochemical properties, improving the descriptor's effectiveness in structural analysis. Furthermore, regression models are developed to predict the energetic behavior of high-dimensional kekulene structures, offering a robust framework for advanced studies in molecular stability and design.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 8","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143793622","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical Study on the Evolution Mechanism of NOX and COX During the Pyrolysis of Nitric Acid and Glucopyranose","authors":"Ye Hong,&nbsp;Mingkai Guo,&nbsp;Lang Liu,&nbsp;Keqian Zhang,&nbsp;Cheng He,&nbsp;Hua Zhang","doi":"10.1002/qua.70044","DOIUrl":"https://doi.org/10.1002/qua.70044","url":null,"abstract":"<div>\u0000 \u0000 <p>Sugar, as a denitration agent, has broad application prospects in the field of high-level radioactive liquid waste (HLLW) treatment. Understanding the interaction mechanism between nitric acid and sugar is crucial for the development of HLLW treatment. This study presents a detailed reaction mechanism, revealing key intermediates (HNO₂) and pathways (generation of carboxyl groups) leading to critical products (NO₂, NO, CO₂, and CO). The work shows five different paths leading to the ring-opening of β-D-glucopyranose. The results indicate that the ring-opening path involving the interaction of H₃O⁺ with glycosidic oxygen has the greatest kinetic advantage, with lower energy of highest point (EHP) (63.6 kJ/mol) and lower highest energy barrier (HEB) (49.2 kJ/mol). Furthermore, carbon oxides, as key gaseous products, exhibit a synergistic relationship with the generation pathways of nitrogen oxides, promoting each other. In addition, through thermodynamic analysis of the four reaction products (NO₂, NO, CO₂, and CO), the study shows that the reactions producing NO₂ and NO are spontaneous exothermic reactions, while the reactions generating CO₂ and CO are non-spontaneous endothermic reactions. The study aims to elucidate the atomic-scale interaction mechanism between sugar-based denitration agents and nitric acid, providing a theoretical basis for the application of natural polysaccharides in HLLW, while also opening new avenues for the design of reducing agents and byproduct control strategies in industrial denitration processes.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 8","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143786946","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":"Ab Initio Study of the Magnetic and Electronic Properties of C6N6 Nanoribbons","authors":"Adeleh Vatankhahan,&nbsp;Tayebeh Movlarooy","doi":"10.1002/qua.70027","DOIUrl":"https://doi.org/10.1002/qua.70027","url":null,"abstract":"<div>\u0000 \u0000 <p>The effect of ribbon width and edge shape on the electronic and magnetic properties of C₆N₆ nanoribbons has been examined using density functional theory (DFT). The results indicate that all the considered C₆N₆ nanoribbons are energetically stable, and hydrogenation increases their stability while eliminating their magnetic properties. As the ribbon width increases, the energy gap decreases. The findings suggest that the band gap can be tuned by altering the edge shape and ribbon width. Consequently, the studied nanoribbons are promising candidates for optoelectronic and spintronic devices.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 8","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143786945","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":"First-Principles to Explore the Pressure on the Structural, Mechanical, Electronic Structure and Thermodynamic Properties of Nb2C","authors":"Qiang Fan,&nbsp;ShunRu Zhang,&nbsp;HaiJun Hou,&nbsp;Jianhui Yang","doi":"10.1002/qua.70040","DOIUrl":"https://doi.org/10.1002/qua.70040","url":null,"abstract":"<div>\u0000 \u0000 <p>Nb₂C has attracted particular attention in the field of elevated temperature, wear resistance, and corrosion resistance, owing to its unique physical and chemical properties. Currently, fewer efforts have been devoted to the exploration of its mechanical properties and thermodynamic response under elevated pressure. As a solution, theoretical calculations were employed to reveal the influence of increased pressure on the structural, mechanical, electronic, and thermodynamic properties of Nb₂C. Elastic moduli were derived from elastic constants, whereas Poisson's ratio, sound velocity, and Debye temperature were determined using the obtained elastic moduli and constants. The investigation focused on the analysis of elastic anisotropy through the utilization of various indexes for elastic anisotropy, as well as the construction of three-dimensional (3D) surfaces and their planar projections. The analysis of the electronic characteristics indicates that Nb₂C displays a metallic behavior. Moreover, the hardness <i>H</i>_v and thermal conductivity <i>k</i> were evaluated by different methods.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 7","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143761923","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical Study of Structures and Spectral Properties of ScSnn0/−/2− (n = 4–17) Nanoalloy Clusters","authors":"Shuilian Tu,&nbsp;Yanpeng Zhang,&nbsp;Caixia Dong,&nbsp;Zhaofeng Yang,&nbsp;Xueyan Dong,&nbsp;Jucai Yang,&nbsp;Bin Liu","doi":"10.1002/qua.70039","DOIUrl":"https://doi.org/10.1002/qua.70039","url":null,"abstract":"<div>\u0000 \u0000 <p>The ground-state structures of neutral, monovalent, and divalent anion ScSn_<i>n</i>^0/−/2− (<i>n</i> = 4–17) clusters were calculated by using a global search technique combined with density functional theory, and their spectral properties, electronic configurations, and relative stability were also studied. It is found that the ground-state structures for monovalent anion ScSn_<i>n</i>⁻ (<i>n</i> = 4–17) clusters are similar to those of divalent anions, and the ground-state structures for ScSn_<i>n</i>^−/2− are all adsorption structures obtained by adsorbing one Sn atom on the structures of ScSn_<i>n</i>−1^−/2−. The growth mode of ScSn_<i>n</i>^0/−/2− (<i>n</i> = 4–17) clusters can be divided into three different types of adsorption modes (<i>n</i> = 4–5, <i>n</i> = 6–10 and <i>n</i> = 11–17): ScSn₄^0/−/2− triangular bipyramid structures, ScSn₆^0/−/2− pentagonal bipyramid structures, and ScSn₁₁^0/−/2− single capped anti-pentagonal prism structures are used as base units to adsorb 1–6 Sn atoms, forming adsorption structures. When <i>n</i> = 11, it is the smallest cage structure size. The simulated photoelectron spectra of ScSn_<i>n</i>⁻ clusters are in good agreement with the existing experimental spectra. The infrared, Raman, and ultraviolet spectral properties of ScSn_<i>n</i>^0/−/2− (<i>n</i> = 4–17) clusters were analyzed, and their natural population analysis, dissociation energy, second-order energy difference, and HOMO-LUMO energy gap were also discussed. The results show that the FK-structure ScSn₁₆⁻ cluster not only has good thermodynamic stability and chemical stability, but also exhibits ideal optical properties, which can be used as a potential nano-optical material building block.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 7","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143749642","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":"Research on the Mechanism of the Influence of Chromium and Nitrogen Elements on the Formation of the Passivation Film on the Surface of High-Nitrogen Steel","authors":"Kai Ning,&nbsp;Feng Miao,&nbsp;Fengde Liu,&nbsp;Hong Zhang","doi":"10.1002/qua.70037","DOIUrl":"https://doi.org/10.1002/qua.70037","url":null,"abstract":"<div>\u0000 \u0000 <p>The excellent corrosion resistance of high-nitrogen steel is related to the passivation film on its surface. However, the mechanism by which nitrogen and chromium atoms affect the formation of the passivation film remains unclear. Electrochemical test results show that nitrogen and chromium promote the formation of the passivation film and secondary passivation. The calculation results indicate that oxygen atoms tend to adsorb on the Fe(111) surface, and chromium doping enhances the adsorption of oxygen atoms. Nitrogen doping increased the segregation energy of chromium toward the surface by 79.8%, promoting the segregation of chromium toward the surface, which further enhanced the adsorption of oxygen atoms on the Fe(111) surface. The synergistic effect of nitrogen and chromium causes oxygen atoms to rapidly accumulate on the Fe(111) surface, forming a protective passivation film, which is the fundamental source of corrosion resistance. In addition, the d-band center is positively correlated with oxygen adsorption energy, indicating that increasing the d-band center on the surface can enhance the adsorption of oxygen atoms, promote the formation of passivation films, and improve corrosion resistance. These findings provide theoretical insights and strategies for studying and controlling the corrosion resistance of materials.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 7","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143749683","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical Simulation Degradation of Bromoxynil by Ozonation in Liquid Phase: Mechanism Pathways, Kinetics, and Ecotoxicity","authors":"Ruijun Chu,&nbsp;Zia UI Haq Khan,&nbsp;Yuquan Zhu,&nbsp;Rufang Zhao,&nbsp;Wenzhong Wu,&nbsp;Jingyu Sun","doi":"10.1002/qua.70041","DOIUrl":"https://doi.org/10.1002/qua.70041","url":null,"abstract":"<div>\u0000 \u0000 <p>Ozonation has been identified as an effective technique to degrade benzene pollutants in the wastewater environment. Bromoxynil, widely employed in agriculture, poses a serious environmental concern. This study presents a comprehensive theoretical investigation of the bromoxynil and ozone reactions using high-level quantum chemical calculations, transition state theory simulations, and computational toxicology in the liquid phase. The bromoxynil and O₃ reaction follows the Criegee mechanism by forming primary ozonides (POZs). Density functional theory calculations indicated that the ozone addition to C3C4, C4C5, and C5C6 positions of the benzene ring of bromoxynil is predominant, forming the primary ozonides IM3, IM4, and IM5, respectively. IM4 is the most important primary ozonide, which predominantly yields the CI7 and CI8 Criegee intermediates. The formation pathways of POZs IM3 and IM5 compete with IM4; then IM3 and IM5 decompose into CI5, CI6, CI9, and CI10. The subsequent reaction channels of CI8 and CI10 include their further reactions with O₃, O₂, and H₂O. Transition state theory simulations based on the potential energy surfaces calculated here for the bromoxynil + O₃ reaction indicate that the IM4 reaction yields 42.69% at 298 K, and the branching fractions of IM3 and IM5 are 31.01% and 18.05%, respectively. According to the results of toxicity assessment, the acute and chronic toxicity of most degradation intermediates and byproducts are lower than bromoxynil for aquatic organisms after ozonolysis. The studied reaction mechanisms directly link the kinetics and toxicity of bromoxynil degradation. Our results have provided significant data for the degradation of bromoxynil, which are discussed.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 7","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726834","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":"Determination of Molecular Symmetry Adapted Eigenroots in the Variational Quantum Eigensolver Framework","authors":"Dibyendu Mondal,&nbsp;Rahul Maitra","doi":"10.1002/qua.70029","DOIUrl":"https://doi.org/10.1002/qua.70029","url":null,"abstract":"<div>\u0000 \u0000 <p>Variational Quantum Eigensolver (VQE) provides a lucrative platform to determine molecular energetics in near-term quantum devices. While the VQE is traditionally tailored to determine the ground state wavefunction with the underlying Rayleigh-Ritz principle, for molecules characterized by a given point group symmetry, we propose to unify the VQE framework to treat the lowest energy states of any irreducible representation and spin-multiplicity. The method relies on the construction of a symmetry adapted multi determinantal reference where the constituent determinants are entangled through appropriate Clebsch-Gordan coefficients to ensure the desired spin-multiplicity. The unitary operator, defined in terms of totally symmetric spin-free generators, safeguards the method against variational collapse to symmetry broken solutions. We also propose an energy sorting based adaptive ansatz construction algorithm starting from a pool of totally symmetric spin-free unitary generators to come up with dynamically optimal ansatz. The proposed methodology allows us to build up further search algorithms within a reduced dimensional symmetry-adapted sub-Hilbert-space. With a highly compact circuit structure, it is expected to be realized in the near-term quantum devices to study emerging chemical phenomena and exploration of novel chemical space.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 7","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143717033","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":"Physical Mechanisms of Linear and Nonlinear Spectra of All-Benzene Catenane and Trefoil Knots Based on the First Principle","authors":"Zhiyuan Yang,&nbsp;Xinwen Gai,&nbsp;Chuanqiang Fan,&nbsp;Wanbin Ran,&nbsp;Jingang Wang","doi":"10.1002/qua.70033","DOIUrl":"https://doi.org/10.1002/qua.70033","url":null,"abstract":"<div>\u0000 \u0000 <p>In this study, we investigate the physical mechanisms underlying the linear and nonlinear optical spectra of all-benzene catenane and trefoil knot structures using first-principles calculations based on density functional theory (DFT). Our results reveal significant variations in electrostatic potential, electronic structures, and photon absorption characteristics across the three topological molecules. The energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the molecules is different, which affects the ability of electron transitions. One-photon absorption (OPA) and two-photon absorption (TPA) spectra were analyzed through transition density matrix (TDM) and electron-hole density diagrams, demonstrating distinct electronic transitions and charge transfer characteristics. Additionally, Raman and resonance Raman spectroscopies, coupled with vibrational mode analysis, provide insight into the nonlinear optical properties of these molecules. Magnetically induced current density analyses further reveal substantial electronic delocalization, emphasizing the role of π-conjugation in their optical responses. This work provides a theoretical foundation for advancing the use of topological carbon nanomaterials in optoelectronics and nonlinear optics.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 7","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699038","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":"Atomic Radii Derived From the Expectation Value \u0000 \u0000 \u0000 \u0000 \u0000 r\u0000 4\u0000 \u0000 \u0000 \u0000 $$ leftlangle {r}^4rightrangle $$","authors":"Gerrit-Jan Linker,&nbsp;Marcel Swart,&nbsp;Piet Th. van Duijnen","doi":"10.1002/qua.70032","DOIUrl":"https://doi.org/10.1002/qua.70032","url":null,"abstract":"<div>\u0000 \u0000 <p>The atomic radius as a fundamental chemical descriptor for the size of a chemical element is often used in physical chemistry. Many reference sets are available, based either on experiment or calculations. For example, Alvarez compiled a set of consistent van der Waals radii (<i>Dalton Trans.</i> <b>2013</b>, <i>42</i>, 8617) based on millions of measured interatomic non-bonded distances. In quantum mechanics, there are many ways in which the atom size can be defined and obtained because the atomic radius is not an observable. Here, we show that a theoretical measure can be based on expectation values such as <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mfenced>\u0000 <msup>\u0000 <mi>r</mi>\u0000 <mn>2</mn>\u0000 </msup>\u0000 </mfenced>\u0000 </mrow>\u0000 <annotation>$$ leftlangle {r}^2rightrangle $$</annotation>\u0000 </semantics></math> and <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mfenced>\u0000 <msup>\u0000 <mi>r</mi>\u0000 <mn>4</mn>\u0000 </msup>\u0000 </mfenced>\u0000 </mrow>\u0000 <annotation>$$ leftlangle {r}^4rightrangle $$</annotation>\u0000 </semantics></math>. These are easily obtained from atomic electric moments, routinely generated by popular quantum chemistry codes, with full control over electronic structure, charge, spin state, etc. As such we obtain a measure for the size of free atoms H to Xe and demonstrate linear scaling of atomic size in the series as outermost <i>s</i>, <i>p</i> or <i>d</i> subshells are filled according to the Madelung rule. Radii derived from <span></span><math>\u0000 <semantics>\u0000 <mrow>\u0000 <mfenced>\u0000 <msup>\u0000 <mi>r</mi>\u0000 <mn>4</mn>\u0000 </msup>\u0000 </mfenced>\u0000 </mrow>\u0000 <annotation>$$ leftlangle {r}^4rightrangle $$</annotation>\u0000 </semantics></math> compare best to Alvarez's empirical reference set of van der Waals radii, and atomic radii from theoretical sources. Known periodic trends of atomic radii are well reproduced by our data. Furthermore, we demonstrate the dependence of atomic size on the electronic structure and spin state for <i>d</i>-block elements.</p>\u0000 </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":"125 7","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143689636","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}