Computational and Theoretical Chemistry最新文献

{"title":"Comparison of protonation and anion binding preference of Chatt-type tungsten dinitrogen complex: DFT studies","authors":"Pennarasi Natarajan ,&nbsp;Hilal Ahmad Khan ,&nbsp;Deepa Masilamani","doi":"10.1016/j.comptc.2024.115010","DOIUrl":"10.1016/j.comptc.2024.115010","url":null,"abstract":"<div><div>In this paper, preference of protonation and anion binding to Chatt-type tungsten complex [W(Ph₂(CH₂)₂Ph₂)₂(N₂)₂] was investigated. Optimization of metal complexes [W(PH₂(CH₂)₂PH₂)₂(N₂)₂], [W(PH₂(CH₂)₂PH₂)₂N₂FH], [W(PH₂(CH₂)₂PH₂)₂(N₂)₂H] and [W(PH₂(CH₂)₂PH₂)₂N₂F] was carried out using density functional theory (DFT). Diethyl ether solution of HBF₄ was used as a proton source. DFT calculations were carried out to understand the reactivity pattern shown by Chatt-type dinitrogen (N₂) complex. Thermodynamic energy values for the protonation of coordinated dinitrogen followed by anion binding; anion binding followed by protonation; and simultaneous reaction of protonation of dinitrogen and anion binding have been calculated. The energy values revealed that the protonation of dinitrogen followed by anion binding is preferable over anion binding followed by protonation.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115010"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160007","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":"DFT insights on lead-free double perovskite A2(Ag/In)BrO6 (A=Ca, Sr, Ba) phase for optoelectronic applications","authors":"D.S. Jayalakshmi ,&nbsp;V. Dharshini ,&nbsp;Bhuvanesh Srinivasan ,&nbsp;R. Gopalan ,&nbsp;D. Hemanand","doi":"10.1016/j.comptc.2025.115075","DOIUrl":"10.1016/j.comptc.2025.115075","url":null,"abstract":"<div><div>The first principle investigation on the structural, electronic, optical, thermal and thermoelectric properties of lead-free double perovskite A₂(Ag/In)BrO₆ (A=Ca, Sr, Ba) in the cubic phase has been performed using the Full Potential Linearized Augmented Plane Wave (FP-LAPW) method in the framework of DFT (Density Functional Theory). The computational structural properties shows the most stable structure in the phase group of Fm3m (225) for the proposed compounds A₂(Ag/In)BrO₆ (A=Ca, Sr, Ba). Modified Becke–Johnson (mBJ) potential embedded in the WIEN2K code is used to calculate the band structure. The obtained band structure plots and Density of State histograms depicts that the proposed materials are conductor or slightly the stage ahead from semiconductor whereas the parent material namely Ba₂NaBrO₆ is a direct band gap semiconductor. The total and partial density of states shows that the electron contribution towards the Fermi region is predominant due to O-p orbitals, Ag-d orbitals and In-p orbital. There is a negligible contribution arising from the alkaline earth metals namely Ba, Sr and Ca. In view of optical properties analysis, the parameters such as refractive index, dielectric function, reflectivity, optical conductivity exhibits strong absorption of photons and great potential to conduct electrons in the UV region whereas Ba₂InBrO₆ has fascinating optical properties in the UV region. Hence, among these six novel compounds, Ba₂InBrO₆ has the preferable photovoltaic performance and conversion efficiency, making it has the potential candidate of photovoltaic application in the UV region. The thermoelectric properties such as Seebeck coefficient, power factor and thermoelectric figure of merit are computed to all the proposed compounds and found Ba₂NaBrO_6, Ca₂AgBrO₆ are more efficient due to its remarkable obtained power factor.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115075"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160054","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 study of the Mn-alloyed Cr2Ge2Te6 monolayer: Intrinsic ferromagnet with robust half-metallicity and large magnetic anisotropy energy","authors":"Xu-li Wang ,&nbsp;Hua Chen ,&nbsp;Jing-jing Xie ,&nbsp;Ling Yan ,&nbsp;Ye-hui Zhang ,&nbsp;Jin Lv ,&nbsp;Bing Wang ,&nbsp;Hai-shun Wu","doi":"10.1016/j.comptc.2024.115057","DOIUrl":"10.1016/j.comptc.2024.115057","url":null,"abstract":"<div><div>Two-dimensional (2D) materials with intrinsic half-metallicity and large magnetic anisotropy energy (MAE) have been a long-sought goal because of potential applications in high-performance spintronics. In this work, using first-principles calculations, we design, investigate and find that the Mn-alloyed Cr₂Ge₂Te₆ monolayer is a half-metal with a considerable in-plane magnetic anisotropy energy (IMAE, 2.276 meV/unitcell) and a high Phase-Transition temperature (Tc/185 K), which is about 3 times higher than that of Cr₂Ge₂Te₆ monolayer without introducing any carriers. Meanwhile, according to the second-order perturbation theory, the IMAE is revealed mainly origin from the couplings of <span><math><mrow><mo>〈</mo><msub><mi>p</mi><mi>y</mi></msub><mo>↑</mo><mfenced><mrow><msub><mi>L</mi><mi>x</mi></msub></mrow></mfenced><msub><mi>p</mi><mi>z</mi></msub><mo>↓</mo><mo>〉</mo></mrow></math></span> and <span><math><mrow><mo>〈</mo><msub><mi>p</mi><mi>y</mi></msub><mo>↓</mo><mfenced><mrow><msub><mi>L</mi><mi>x</mi></msub></mrow></mfenced><msub><mi>p</mi><mi>z</mi></msub><mo>↑</mo><mo>〉</mo></mrow></math></span> of Te atom and the couplings of <span><math><mrow><mo>〈</mo><msub><mi>d</mi><mrow><msup><mrow><mi>x</mi></mrow><mn>2</mn></msup><mo>-</mo><msup><mrow><mi>y</mi></mrow><mn>2</mn></msup></mrow></msub><mo>↑</mo><mfenced><mrow><msub><mi>L</mi><mi>z</mi></msub></mrow></mfenced><msub><mi>d</mi><mrow><mi>x</mi><mi>y</mi></mrow></msub><mo>↑</mo><mo>〉</mo></mrow></math></span> and <span><math><mrow><mo>〈</mo><msub><mi>d</mi><mrow><msup><mrow><mi>x</mi></mrow><mn>2</mn></msup><mo>-</mo><msup><mrow><mi>y</mi></mrow><mn>2</mn></msup></mrow></msub><mo>↓</mo><mfenced><mrow><msub><mi>L</mi><mi>z</mi></msub></mrow></mfenced><msub><mi>d</mi><mrow><mi>x</mi><mi>y</mi></mrow></msub><mo>↓</mo><mo>〉</mo><mspace></mspace></mrow></math></span> of Mn atom. Besides, the ferromagnetism of the CrMnGe₂Te₆ monolayer can be further improved by tensile strains and hole doping. Our findings suggest this monolayer would be a good candidate for spintronic devices and we would provide a strategy for designing the excellent spintronic materials.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115057"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160077","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 the global and local aromaticity of BN-Substituted naphthalene analogues","authors":"Tursunjan Aydan,&nbsp;Ablikim Kerim","doi":"10.1016/j.comptc.2025.115080","DOIUrl":"10.1016/j.comptc.2025.115080","url":null,"abstract":"<div><div>The topological resonance energy (TRE) method was employed to investigate the aromaticity of BN-substituted naphthalene molecules. To study the local aromaticity of the BN-substituted naphthalenes, the bond resonance energy (BRE) and circuit resonance energy (CRE) indices were applied. The Hückel-London ring current (RC) model was used to assess the aromaticity of the individual rings in the BN-substituted naphthalenes. The local aromatic states of the individual rings, as indicated by the BRE and CRE indices, correspond directly with the RC results, which reflect the strength of diatropic currents within those rings.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115080"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160087","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 Si/C mixed analogues of platonic hydrocarbons","authors":"Tamotsu Uchiyama ,&nbsp;Taiji Nakamura ,&nbsp;Miyabi Hiyama ,&nbsp;Takako Kudo","doi":"10.1016/j.comptc.2025.115116","DOIUrl":"10.1016/j.comptc.2025.115116","url":null,"abstract":"<div><div>In a continuation of our research on the Si/C mixing effect for various organic compounds, we systematically investigated the Si/C mixed analogues of saturated Platonic hydrocarbons, tetrahedrane, cubane, and dodecahedrane, by ab initio molecular orbital calculations. The molecular framework of these compounds comprises distorted sp³ hybridized carbon and silicon atoms, so strain energy is expected to be a crucial factor controlling the properties. Therefore, we investigated the structure, strain energy, and relative stability of the isomers with various Si/C arrangements for the compounds. We then compared the strain energy changes against the Si ratio and clarified the Si/C mixing effect on the saturated Platonic polyhedral compounds.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115116"},"PeriodicalIF":3.0,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138428","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":"Kinetic study of concerted HO2 elimination reactions of α,β-hydroxyalkylperoxy radicals in alcohols and alkenes combustion mechanism","authors":"Siyu Chen ,&nbsp;Nan Kang ,&nbsp;Quan Zhu ,&nbsp;Zerong Li","doi":"10.1016/j.comptc.2025.115123","DOIUrl":"10.1016/j.comptc.2025.115123","url":null,"abstract":"<div><div>HO₂ elimination reactions in hydroxyalkylperoxy (HOROO) radicals are crucial in low-temperature combustion of alcohols and alkenes, as they compete with the intramolecular H-migration reaction, affecting HO₂ production and oxidation rates. This study investigates the kinetics of HO₂ elimination reactions from α- and β-HOROO radicals, categorizing them based on the carbon type attached to the peroxy group and the hydroxyl position. Quantum calculations are performed at wB97XD/ma-TZVP//M06-2x/6–311 + G(d,p) with 1-D hindered rotor corrections. High-pressure and pressure-dependent rate constants are calculated via TST and RRKM/ME methods. Our findings yield three main conclusions: (1) wB97XD gives rate constants close to benchmark CCSD(T), with a maximum overestimation factor of 2.06; (2) using kinetic data from alkanes to alcohols or alkenes can sometimes result in errors exceeding an order of magnitude; and (3) pressure dependence becomes significant at temperatures above 800 K. The study offers accurate high-pressure limit rate rules and pressure-dependent expressions, which are essential for refining combustion mechanisms in alcohol and alkene oxidation models.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115123"},"PeriodicalIF":3.0,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143348700","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 comprehensive study of 4,4′-bis (4-pyridyl) terphenyl self-assembled structures on highly oriented pyrolytic graphite: Morphology and electronic properties","authors":"Fernando R. Pantano ,&nbsp;Franco M. Eroles ,&nbsp;Fernando P. Cometto ,&nbsp;Mariana I. Rojas","doi":"10.1016/j.comptc.2025.115122","DOIUrl":"10.1016/j.comptc.2025.115122","url":null,"abstract":"<div><div>Scanning tunneling microscopy (STM) was used to observe the adsorption structure of 4,4′-bis (4-pyridyl) terphenyl (BPTB) molecules self-assembled on highly oriented pyrolytic graphite (HOPG). The STM images revealed various polymorphic structures, such as flat and curved configurations, which were further investigated and validated through first-principles atomistic simulations. The interactions between the BPTB molecules and the HOPG substrate were analyzed in detail, particularly in relation to their adsorption orientations on the graphene surface. Additionally, the electrical and optical properties of the resulting films and the BPTB/graphene heterojunction were examined, highlighting their potential applications in the development of optoelectronic devices.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115122"},"PeriodicalIF":3.0,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143328311","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 theoretical quest for laetrile drug delivery by neutral, cationic, and anionic gold nanoparticles","authors":"Somayeh Safaei ,&nbsp;Ameneh Cheshmehkani ,&nbsp;Mohamad Zaman Kassaee","doi":"10.1016/j.comptc.2025.115105","DOIUrl":"10.1016/j.comptc.2025.115105","url":null,"abstract":"<div><div>Interactions of laetrile (D-mandelonitrile-β-glucuronide, <strong>1</strong>) with neutral (Au₃), cationic (Au₃⁺), and anionic (Au₃⁻) gold nanoparticles are studied by the density functional theory (B3LYP/6–311++G(d,p) <span><math><mo>∪</mo></math></span>LANL2DZ). Interaction of <strong>1</strong> and gold trimer nanoparticles occur between the Au atom and the O, N, and C atoms of <strong>1</strong>, or through the unconventional Au…H–O hydrogen bonding. Depending on the charge on the gold nanoparticle, these bonds may contribute differently to the formation of the complex. Binding energy calculations indicate that the neutral Au nanoparticles have the lowest, while cationic Au₃⁺ nanoparticles have the highest affinity for interaction with <strong>1</strong>. Natural population analysis and charge transfers in the complexes are assessed by the natural bond orbital (NBO). Quantum theory of atoms in molecules (QTAIM) is also applied to interpret the nature of the bonding interactions.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115105"},"PeriodicalIF":3.0,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143328313","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The first-principle study of the interaction of the functionalized boron nitride nanotubes via Pd doping and Pd adsorption towards 2,3,7,8-tetrachlorodibenzo-p-dioxin","authors":"Ruoxi Wang ,&nbsp;Rongxiu Zhu ,&nbsp;Dongju Zhang","doi":"10.1016/j.comptc.2025.115106","DOIUrl":"10.1016/j.comptc.2025.115106","url":null,"abstract":"<div><div>In order to explore the applications of boron nitride nanotubes (BNNTs) in pollutant detection and removal, we perform two modified methods to functionalize BNNTs via Pd doping and Pd adsorption, and further investigate the adsorption interaction of these functionalized BNNTs towards highly toxic 2,3,7,8-tetrachlorodibenzo-<em>p</em>-dioxin (TCDD) by density functional theory (DFT) calculations. The results revealed that both Pd doping and Pd adsorption induce new impurity electronic states and improve the conductive performance of the BNNTs. However, the BNNT with Pd doping has notable distinctions in the DOS and spin DOSs compared to the BNNT with Pd adsorption, and particularly the former occurs spontaneous magnetization. These two functionalized BNNTs present the larger adsorption energy, clear electron density overlap and significant changes of DOSs towards TCDD with the respective electronic response signals compared with the pristine BNNT. These findings offer new possibilities to functionalize BNNTs via Pd doping or Pd adsorption to detect or remove dioxin.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115106"},"PeriodicalIF":3.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138429","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":"Thermochemistry of demethylation of methoxy groups in aromatic compounds: Applicability of DFT, G4, and G4(MP2) methods","authors":"Andrea Kováčová ,&nbsp;Matej Uhliar ,&nbsp;Dušica Simijonović ,&nbsp;Edina H. Avdović ,&nbsp;Vladimír Lukeš ,&nbsp;Zoran Marković ,&nbsp;Erik Klein","doi":"10.1016/j.comptc.2025.115104","DOIUrl":"10.1016/j.comptc.2025.115104","url":null,"abstract":"<div><div>This work analyses O<img>C bond dissociation enthalpies (BDE) of aromatic compounds. BDE values were calculated for 23 <em>meta</em>- and <em>para</em>-substituted anisoles, together with polymethoxybenzenes and naturally occurring coumarins, using three theoretical methods: M06-2X, G4, and G4(MP2). Electron-donating groups decrease the O<img>C BDE values, while electron-withdrawing groups increase them. The G4 and M06-2X methodologies show excellent agreement with experimental data, although M06-2X tends to overestimate BDEs. The applicability of other functionals was also assessed. G4 data for studied anisoles and phenols confirm that substituent effect on O<img>C BDEs of anisoles and O<img>H BDEs of phenols is identical. Found Hammett-type dependences can be employed for the gas-phase BDE estimations for anisoles and phenols possessing other substituents with known <em>σ</em>_m and <em>σ</em>_p⁺ constants. Obtained results also emphasize the accuracy and computational efficiency of the G4(MP2) method and its applicability for the investigation of demethylation thermochemistry of larger molecules.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1245 ","pages":"Article 115104"},"PeriodicalIF":3.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142896","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}