Computational and Theoretical Chemistry最新文献

{"title":"Potassium decoration on graphenyldiene monolayer for advanced reversible hydrogen storage","authors":"José A.S. Laranjeira ,&nbsp;Nicolas F. Martins ,&nbsp;Kleuton A.L. Lima ,&nbsp;Bill. D. Aparicio-Huacarpuma ,&nbsp;Luiz A. Ribeiro Junior ,&nbsp;Xihao Chen ,&nbsp;Douglas S. Galvao ,&nbsp;Julio R. Sambrano","doi":"10.1016/j.comptc.2025.115504","DOIUrl":"10.1016/j.comptc.2025.115504","url":null,"abstract":"<div><div>Potassium-decorated graphenyldiene (K@GPD) is investigated as a promising two-dimensional material for reversible hydrogen storage using first-principles density functional theory calculations. Potassium atoms bind strongly to the GPD monolayer, and ab initio molecular dynamics (AIMD) simulations confirm the thermal stability of the functionalized system at 300 K. Hydrogen adsorption energies range from -0.11 to -0.14 eV per H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>, denoting reversible storage. At full coverage (18 H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> molecules), the system reaches a storage capacity of 8.82 wt%, exceeding the U.S. DOE target. AIMD simulations reveal spontaneous H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> desorption at ambient temperature, demonstrating excellent reversibility.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115504"},"PeriodicalIF":3.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217371","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":"Enhanced thermal stability in nitrogen-containing gold carbide cages: A DFT study of Au30N20C60 vs. Au30C20C60","authors":"Jing-Jing Guo ,&nbsp;Hong-Man Ma ,&nbsp;Peng-Bo Liu ,&nbsp;Yi-Sha Chen ,&nbsp;Hui-Yan Zhao ,&nbsp;Jing Wang ,&nbsp;Ying Liu","doi":"10.1016/j.comptc.2025.115513","DOIUrl":"10.1016/j.comptc.2025.115513","url":null,"abstract":"<div><div>Two typical deltoidal hexecontahedron-like gold carbide clusters of Au₃₀N₂₀C₆₀ and Au₃₀C₂₀C₆₀ cages have been constructed under BP86/6-31 g(d) for C, N atoms and BP86/def2-TZVPP for Au atoms in this work. No imaginary frequencies have been found in the vibrational frequency analysis for Au₃₀N₂₀C₆₀ and Au₃₀C₂₀C₆₀ cages. The simulated IR and Raman spectrum may also provide theoretical basis for further exploration. Molecular dynamics simulations show that the highest temperature at which Au₃₀N₂₀C₆₀ maintains its original configuration and subunits after 20 <em>ps</em> NVT MD simulations is 1200 K, which is significantly higher than the 900 K observed for Au₃₀C₂₀C₆₀, indicating that the doped N atoms enhance the thermodynamic stability of gold-carbide clusters. The electronic properties of Au₃₀N₂₀C₆₀ has been discussed via density of states, electron density, and adaptive natural density partitioning, which can clearly explain its electronic behavior.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115513"},"PeriodicalIF":3.0,"publicationDate":"2025-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217366","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":"An intuitive computational method for studying electrostatic interactions of functional groups within difunctional molecules: A case of glycine","authors":"Tianlong Li ,&nbsp;Muhammad Umar Majeed ,&nbsp;Khalil Hassnain ,&nbsp;Wenkang Sun ,&nbsp;Yuzhu Liu","doi":"10.1016/j.comptc.2025.115500","DOIUrl":"10.1016/j.comptc.2025.115500","url":null,"abstract":"<div><div>Research aimed at elucidating the interactions between functional groups within molecules have confronted challenges. This study introduces an innovative computational method to investigate the subtle electrostatic interactions between functional groups within molecules, using glycine as a model system. By combining quantum chemical calculations with molecular dynamics simulations, the present study provides a semi-quantitative approach to assess the impact of internal interactions on molecular properties while conserving computational resources. By comparing with mainstream approaches, the advantages and limitations of this method are elucidated. The results demonstrate that, the internal interactions significantly influence glycine's stability and reactivity, with findings suggesting that this method can be extended to other difunctional molecules.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115500"},"PeriodicalIF":3.0,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217373","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":"Group Fukui potential as a measure of the molecular polarizability","authors":"Savaş Kaya,&nbsp;Nazlı Tutar","doi":"10.1016/j.comptc.2025.115515","DOIUrl":"10.1016/j.comptc.2025.115515","url":null,"abstract":"<div><div>In the present study, we introduced a new method based on group Fukui potential to compute the polarizabilities of organic chemical systems. Here group Fukui potential, <em>ν</em> (<em>f</em>)_GROUP was defined as the sum of the Fukui potentials of atoms, ν(<em>f</em>)_i in the structure of the molecule as: <span><math><mi>ν</mi><msub><mfenced><mi>f</mi></mfenced><mtext>GROUP</mtext></msub><mo>=</mo><munderover><mo>∑</mo><mrow><mi>i</mi><mo>=</mo><mn>1</mn></mrow><mi>N</mi></munderover><mi>ν</mi><msub><mfenced><mi>f</mi></mfenced><mi>i</mi></msub></math></span>. Here, <em>N</em> stands for the number of the atoms in the molecule. The performed analyses proved that there is a reliable relation between polarizability and group Fukui potential and polarizabilities (α_M) of organic molecules. Using equation <span><math><msub><mi>α</mi><mi>M</mi></msub><mo>=</mo><msub><mi>c</mi><mn>1</mn></msub><mi>ν</mi><msub><mfenced><mi>f</mi></mfenced><mtext>GROUP</mtext></msub><mo>+</mo><msub><mi>c</mi><mn>2</mn></msub></math></span>, molecular polarizabilities can be accurately and fast predicted. In the given equation, <em>c</em>_<em>1</em> and <em>c</em>_<em>2</em> are constants that take different numerical values for different groups of organic molecules. The proposed method provides compatible results with the results obtained by experimental tools and previously published theoretical methods. In addition, the correlations obtained support the idea that group Fukui potential is also minimized like polarizability in stable states.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115515"},"PeriodicalIF":3.0,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217409","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":"Crystal structures and stabilities of InxGa1-xN and Mg-doped InxGa1-xN: A first-principles calculation","authors":"Zhigang Lu ,&nbsp;Jianfeng Pan ,&nbsp;Hong Zhang ,&nbsp;Chao Jiang ,&nbsp;Lu Qingbo ,&nbsp;Wenming Yang","doi":"10.1016/j.comptc.2025.115516","DOIUrl":"10.1016/j.comptc.2025.115516","url":null,"abstract":"<div><div>The ground-state configurations and electronic characteristics of InGaN crystals with varying In compositions and their p-type doped counterparts were investigated. A first-principles computational framework was implemented in CASTEP, with its reliability validated through direct comparison with prior experimental data. The calculations demonstrate that the structural stabilities of In_xGa_1-xN and In_xGa_1-xN:Mg crystals are predominantly governed by the type of constituent atoms, while lattice site occupancy exerts relatively minor influence on structural stability.‌ Bonding mechanisms of In_xGa_1-xN and In_xGa_1-xN:Mg crystals were revealed and analyzed, finding that these heteronuclear bonds predominantly arise from orbital hybridization between metal sp-states and nitrogen p-states. Furthermore, it is revealed that the decreasing stability with increasing In content originates from a twofold mechanism: a chemical substitution effect and a universal “expansion effect” caused by lattice strain. This work provides a fundamental explanation for the instability of In-rich nitrides, offering a theoretical foundation for the design of optoelectronic devices.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115516"},"PeriodicalIF":3.0,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145154838","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":"Electronic and structural effects of MgO(100) support on CO adsorption in coinage metal hexamers","authors":"Jonathan C. Luque-Ceballos ,&nbsp;Alessandro Fortunelli ,&nbsp;Alvaro Posada-Amarillas","doi":"10.1016/j.comptc.2025.115499","DOIUrl":"10.1016/j.comptc.2025.115499","url":null,"abstract":"<div><div>We present a comprehensive DFT investigation of CO adsorption on six-atom coinage metal clusters (Cu₆, Ag₆, Au₆) and their bimetallic analogues (Ag₃Cu₃, Au₃Cu₃, Au₃Ag₃), both in the gas phase and supported on a MgO(100) surface. Global optimization techniques were employed to identify the most stable geometries. Upon adsorption, pronounced structural rearrangements emerge, particularly in Cu-containing systems, leading to planar-to-3D transitions that enhance orbital hybridization with the CO molecule and modulate charge transfer pathways. Adsorption energies, projected density of states (PDOS), and Bader charge analysis confirm significant support-induced electronic reorganization. Among the studied systems, Ag₃Cu₃ supported on MgO exhibits the most favorable sensing performance, with a recovery time of 2.39 × 10⁻⁵ s and moderate adsorption strength. Overall, the MgO(100) support enhances charge donation to the clusters and stabilizes the adsorbed species, thereby improving sensor response in the supported configurations. These results highlight the critical role of cluster geometry, composition, and support in tuning adsorption behavior and gas sensing performance in coinage metal clusters.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115499"},"PeriodicalIF":3.0,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217372","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 tetraamine–derived Schiff base ligands and their Cu(II) and Zn(II) complexes","authors":"Shilpa Shajan ,&nbsp;G. Muni Hemalatha ,&nbsp;Kandasamy Thirunavukkarasu ,&nbsp;Krishnan Thirumoorthy","doi":"10.1016/j.comptc.2025.115512","DOIUrl":"10.1016/j.comptc.2025.115512","url":null,"abstract":"<div><div>The theoretical quantum chemical methods were employed to design tetraamine–based Schiff bases and investigate their interaction with Cu²⁺ and Zn²⁺ ions. Three ligands were designed from the possible condensation product of [1,1′–biphenyl]–3,4,3′,4′–tetraamine with thiophene–2–carbaldehyde (L1), 2–furaldehyde (L2), and 1H–indole–3–carbaldehyde (L3). The geometric optimizations, in conjunction with interaction analyses, elucidated the pronounced binding affinity of the ligands for metal ions, with Cu(II) complexes displaying a significantly greater affinity in comparison to their Zn(II) analogs. Molecular orbital evaluations suggested robust metal–ligand interactions, whereby Cu(II) complexes demonstrated enhanced stability in contrast to Zn(II) complexes, which indicated increased reactivity, thereby implying a potential for augmented biological efficacy. Electrostatic potential (ESP) mapping further corroborated the binding affinities of the complexes by illustrating the regions of electrostatic interactions. Furthermore, non-covalent interaction (NCI) analysis provided comprehensive insights into the nature and strength of the forces governing metal–ligand binding, revealing that the stronger interactions in Cu(II) complexes account for their enhanced stability. These theoretical insights provide significant direction for prospective experimental investigations of Schiff base metal complexes in the realms of biomedical and catalytic applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115512"},"PeriodicalIF":3.0,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145154839","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":"Study on electronic and optical properties of novel potential photocatalytic water splitting material: Z-scheme blue-P/WSi2N4 vdW heterostructure","authors":"Jianling Zhao ,&nbsp;Shiquan Feng","doi":"10.1016/j.comptc.2025.115506","DOIUrl":"10.1016/j.comptc.2025.115506","url":null,"abstract":"<div><div>In this study, four blue-P/WSi₂N₄ van der Waals (vdW) heterostructures were designed based on the blue-P and WSi₂N₄ monolayers, with the AA-stacking configuration (AA-HS) identified as the most stable. Then we investigated the structural, electronic, and photocatalytic properties of AA-HS via first-principles calculations. Electronic structure analysis reveals it has an indirect bandgap of 1.75 eV (HSE method) and a type-II band alignment, where the valence band maximum (VBM) and conduction band minimum are localized on the blue-P and WSi₂N₄ layers, respectively. A built-in electric field drives <em>Z</em>-scheme charge transfer, suppressing interfacial recombination while preserving redox-active sites. The AA-HS demonstrates strong redox capability, with the VBM of blue-P layer much lower than the O₂/H₂O potentials and the CBM of WSi₂N₄ layer much higher than the H⁺/H₂ potentials, enabling efficient water splitting. The good light absorption ability further confirms its potential as a high-performance <em>Z</em>-scheme photocatalyst</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115506"},"PeriodicalIF":3.0,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145154841","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":"Theranostic potential of metal-doped B36N36 nanocages for β-lapachone delivery: A density functional theory study","authors":"Liyang Guo,&nbsp;Changqi Chen,&nbsp;Yafei Luo,&nbsp;Ke Zuo,&nbsp;Zhaoyuan Guo,&nbsp;Dianyong Tang","doi":"10.1016/j.comptc.2025.115508","DOIUrl":"10.1016/j.comptc.2025.115508","url":null,"abstract":"<div><div>Natural products have long been a valuable source of anticancer leads. β-lapachone (β-Lap), a natural naphthoquinone compound, has been shown to be a promising anticancer candidate, although its low solubility and bioavailability limit its direct application in the clinic. Boron nitride nanocages have emerged as potential nanocarriers for drug delivery due to their high stability and biocompatibility. Here, we employed density functional theory (DFT) to evaluate the potential of transition metal (M = Fe, Co, Ni, Cu, Zn)-doped nanocage B₃₆N₃₆ as a drug carrier for β-Lap delivery. Our results indicated that β-Lap interacts with the B<img>N bonds of the nanocage through its C<img>O group(s). The incorporation of metals effectively enhances the β-Lap adsorption characteristics of B₃₆N₃₆. The encapsulation of metals inside B₃₆N₃₆ was found to be the most stable structure, and the adsorption energy of β-Lap on metal-encapsulated B₃₆N₃₆ (except for Zn) was found to be higher than that on B₃₆N₃₆ in both aqueous and vacuum states. The electron density difference (EDD), spin density, and frontier molecular orbital theory demonstrate electron transfer from metal dopants to C<img>O groups of β-Lap, weakening C<img>O bonds while strengthening C<img>C bonds to stabilize the complex, with metal doping significantly enhancing adsorption efficiency. Atoms-in-molecules (AIM) theory further reveals that metal doping reinforces O<img>B bonds formed between β-Lap and B₃₆N₃₆ into stronger coordination bonds. The independent gradient model based on Hirschfeld division (IGMH) analysis visually confirms the spatial distribution of interaction regions within the system. Overall, Zn-(1) and Fe-(3) doped B₃₆N₃₆ are expected to be promising candidates for delivering β-Lap, with recovery times at body temperature of 26.44 s and 248 s, respectively. This work provides <em>in silico</em> support for further development of metal-doped B₃₆N₃₆ nanocage as a drug delivery system.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115508"},"PeriodicalIF":3.0,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145154837","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":"Optimizing the basis set extrapolation parameter for weak interaction energy calculations using density functional theory","authors":"Yanliang Wu,&nbsp;Zhigang Ni","doi":"10.1016/j.comptc.2025.115495","DOIUrl":"10.1016/j.comptc.2025.115495","url":null,"abstract":"<div><div>Accurate computation of weak interaction energies remains challenging due to basis set superposition error (BSSE) and the need for diffuse functions. While the counterpoise (CP) method is commonly used to correct BSSE, it increases computational cost and complexity. This work assesses the exponential-square-root extrapolation scheme for density functional theory (DFT) calculations of weak interactions. An optimized extrapolation exponent (<em>α</em> = 5.674) was obtained from a training set of 57 complexes and applied to a two-point extrapolation using def2-SVP and def2-TZVPP basis sets. The resulting interaction energies closely match those from CP-corrected ma-TZVPP calculations, with a mean relative error of ~2%. Although slightly less accurate than CP-corrected values, the extrapolation method requires only about half the computational time. Our results also show that diffuse functions are unnecessary for neutral systems when using CP with def2-TZVPP. Validation on the S66, L7, and NIAR20 benchmark sets and across other functionals confirms the method's robustness and transferability.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115495"},"PeriodicalIF":3.0,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217374","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}