Computational and Theoretical Chemistry最新文献

{"title":"Structural and optoelectronic properties of L-Citrulline based systems: An overview through Density Functional theory","authors":"Bruno P. Silva ,&nbsp;José A.S. Silva ,&nbsp;Mauricélio B. da Silva ,&nbsp;Regina C.R. Santos ,&nbsp;Paulo de Tarso C. Freire ,&nbsp;Ewerton Wagner S. Caetano ,&nbsp;Valder N. Freire","doi":"10.1016/j.comptc.2025.115244","DOIUrl":"10.1016/j.comptc.2025.115244","url":null,"abstract":"<div><div>L-citrulline, a non-proteinogenic amino acid, forms a variety of molecular crystal structures, including anhydrous, hydrated states, and different salts. These structures have garnered significant interest owing to their wide-ranging applications and their utility in studying how long-range interactions affect the structural, electronic, and optical characteristics of molecular crystals. A deeper theoretical comprehension of these features could enhance the application of citrulline polymorphs as key components in pharmaceuticals and contribute to the optimization of synthesis and stability processes for therapeutic purposes. Additionally, these insights may unlock new uses in fields such optoelectronics or sensing, based on their electronic structure characteristics. In this study, we utilized Time-Dependent Density Functional Theory (TD-DFT) to probe the electronic structure of L-citrulline at the molecular level, testing various hybrid DFT functionals to pinpoint those that best capture the electronic properties. The PBE0 and HSE06 functionals emerge as particularly effective, providing accurate depictions of the UV/Vis spectrum with errors of 1.25 % and 0.26 % respectively, in predicting absorption peak maxima. For solid-state analysis, we adopted the DFT GGA + TS dispersion corrected approach to obtain detailed structural geometries. Our research reveals that citrulline crystals have band gaps between 4.5 and 5.0 eV, with direct band gaps observed in the δ-, mono-, and dihydrated forms, while the α-form exhibits an indirect band gap. These crystals also demonstrate substantial charge carrier effective masses and notable optical anisotropy, offering valuable insights into the complex electronic and optical behaviors of citrulline systems and paving the way for their potential use in sensor technologies and optoelectronic devices. Finally, to assess crystal stability, phonon calculations were performed. Analyses of phonon dispersion relations and density of states were analyzed, providing further insight into the dynamic stability and lattice vibrational properties of the various citrulline polymorphs.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1249 ","pages":"Article 115244"},"PeriodicalIF":3.0,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143870598","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":"Modulation of the optoelectronic properties of h-BN/ WTe2 heterostructures with different twist angles by biaxial strain","authors":"Jun Zhang ,&nbsp;Hang Xu ,&nbsp;Jiping Hu ,&nbsp;Xiaotian Yang ,&nbsp;Shipei Ji ,&nbsp;Yipu Qu ,&nbsp;Fang Wang ,&nbsp;Juin J. Liou ,&nbsp;Yuhuai Liu","doi":"10.1016/j.comptc.2025.115245","DOIUrl":"10.1016/j.comptc.2025.115245","url":null,"abstract":"<div><div>Constructing a vertical van der Waals heterostructure can effectively regulate the properties of a single 2D material. This paper constructs a vertical h-BN/WTe₂ heterostructure and uses first-principles methods based on density functional theory to explore the effects of twist angle and biaxial strain on its stability, electronic properties, and optical performance. The results show that the twist angle does not change the direct bandgap and type-I band alignment of the h-BN/WTe₂ heterostructure, but it affects the bandgap size and the positions of the conduction band minimum (CBM) and valence band maximum (VBM). The maximum value of the bandgap occurs at twist angles of 8.9° and 51.1°, with a value of 1.21 eV. Additionally, for the h-BN/WTe₂ heterostructure at a twist angle of 0°, the maximum optical absorption coefficient is 9.5 × 10⁵ cm⁻¹ at 5.38 eV. As the twist angle changes from 0° to 8.9° and 30°, the optical absorption spectrum redshifts, and the absorption coefficient decreases. Furthermore, within the strain range of −12 % to +12 %, the bandgap type of the h-BN/WTe₂ heterostructure changes from indirect to direct and then back to indirect, and a semiconductor-metal phase transition also occurs. The research results provide theoretical guidance for the use of the h-BN/WTe₂ heterostructure in optoelectronic devices, aiding its further development in the field of optoelectronic device applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1249 ","pages":"Article 115245"},"PeriodicalIF":3.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143864643","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":"Proton-mediated catalysis in [Ga4L6]12−: Theoretical study of acetal-ketone hydrolysis","authors":"Xuetao Li,&nbsp;Shuang Wang,&nbsp;Bo Zhu,&nbsp;Wei Guan","doi":"10.1016/j.comptc.2025.115246","DOIUrl":"10.1016/j.comptc.2025.115246","url":null,"abstract":"<div><div>Acetal hydrolysis to ketones is a crucial reaction in organic synthesis, typically requiring strongly acidic conditions. This study presents a theoretical investigation of proton-mediated catalysis in the metallocage [Ga₄L₆]¹²⁻. Quantum mechanical and molecular dynamics simulations demonstrate that [Ga₄L₆]¹²⁻ creates an acidic microenvironment within its cavity, enhancing hydrolysis through cationophilic behavior and stabilization of reactive intermediates via hydrogen bonding with cage ligands. The encapsulation of 2,2-dimethoxypropane (DMP) was found to be both kinetically and thermodynamically favorable, as shown by attach-pull-release (APR) simulations. The hydrolysis mechanism suggests that the catalytic efficiency of [Ga₄L₆]¹²⁻ approaches that of traditional acid catalysis, with similar Gibbs energy barriers for key proton transfer steps. Importantly, the optimal pathway involves cooperative interactions among H₃O⁺, water molecules, and the cage structure, lowering hydrolysis energy barriers and suggesting potential sustainable catalytic applications for [Ga₄L₆]¹²⁻.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1249 ","pages":"Article 115246"},"PeriodicalIF":3.0,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143870596","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 of direct Z-scheme water splitting photocatalytic Janus-WSSe/HfZrCO2 vdW heterostructures: First principles calculations","authors":"Shizhuo Wang ,&nbsp;Yifan Ma ,&nbsp;Xuechao Feng ,&nbsp;Yang Yang ,&nbsp;Luogang Xie ,&nbsp;Shiquan Feng","doi":"10.1016/j.comptc.2025.115243","DOIUrl":"10.1016/j.comptc.2025.115243","url":null,"abstract":"<div><div>Due to the retention of the strong redox active sites, 2D <em>Z</em>-scheme heterostructures exhibit many advantages in photocatalytic water splitting for hydrogen production. In this paper, based on Janus-WSSe and HfZrCO₂ monolayers, we designed 24 van der Waals (vdW) WSe₂/HfZrCO₂ heterostructures, and selected out one <em>Z</em>-scheme heterostructure (HS) that most likely to serve as a water splitting photocatalyst for further study. Then, through first principles calculations, the stability, electronic and optical properties and photocatalytic water splitting mechanism for the HS were studied in detail. The results show that it is a promising <em>Z</em>-scheme water splitting photocatalyst in both neutral and acidic environments.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115243"},"PeriodicalIF":3.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143852059","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 insights into novel Ba3MX3 (M = P, Sb; X = F, Cl) perovskites for advanced optoelectronics: A first-principles DFT study","authors":"Md Rabbi Talukder ,&nbsp;Md. Mehedi Hasan ,&nbsp;Nadim Mahmood Nayeem ,&nbsp;Md. Rafiqul Islam ,&nbsp;Jehan Y. Al-Humaidi ,&nbsp;Md Rasidul Islam ,&nbsp;Md Masud Rana","doi":"10.1016/j.comptc.2025.115239","DOIUrl":"10.1016/j.comptc.2025.115239","url":null,"abstract":"<div><div>Non-toxic halide cubic perovskites set the standard for the commercialization of optoelectronic and photovoltaic devices. Because of their enormous importance, a comprehensive analysis of the physical characteristics of cubic Ba₃MX₃ (M = P, Sb; X = F, Cl) perovskites was analyzed in this study utilizing ab initio Density Functional Theory. The thermodynamic stability of the explored materials was validated by negative formation energies, while the simulated XRD spectra firmly solidified that all the perovskites exhibit cubic structures. The GGA-PBE functional unveiled direct band gaps of 0.95 eV, 0.96 eV, 1.07 eV, and 0.99 eV for the semiconducting perovskites Ba₃PF₃, Ba₃PCl₃, Ba₃SbF₃, and Ba₃SbCl₃, respectively. The HSE06 potential unveiled refined band gaps of 1.42 eV, 1.50 eV, 1.96 eV, and 1.89 eV for the respective perovskites, emphasizing their potential as viable options for solar cell technologies. Moreover, the explored materials exhibited excellent absorption, high photoconductivity, an ideal refractive index, lower reflectivity, and minimal loss function in the visible spectrum, rendering them outstanding contenders for solar cell applications. The Born stability benchmarks validated the mechanical stability of all the explored perovskites. Additionally, their inherent stiffness, hardness, toughness, brittleness, and anisotropic behavior are vital for long-term durability in engineering applications. Thermodynamic assessments validated the thermal stability of these perovskites at wide temperature ranges. The study's findings revealed that Ba₃MX₃ (M = P, Sb; X = F, Cl) perovskites could emerge as promising optical materials, and their synthesis in the upcoming days is highly anticipated.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115239"},"PeriodicalIF":3.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835241","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 SiC/WS2 layered heterojunction composite ceramics: Promoting ceramic process design","authors":"Ge Feng","doi":"10.1016/j.comptc.2025.115240","DOIUrl":"10.1016/j.comptc.2025.115240","url":null,"abstract":"<div><div>The advancement of novel ceramic composite materials is advantageous for improving the design quality and performance of ceramic devices. This study utilizes first-principles computational methods to develop SiC/WS₂ heterojunction composite materials, specifically SiC/WS₂, SiC/WS₂/SiC, and WS₂/SiC/WS₂, and examines the modulation of their properties through the application of biaxial and vertical strain. The findings reveal that all three types of SiC/WS₂ heterojunctions exhibit commendable structural stability. Furthermore, each heterojunction displays direct bandgap semiconductor characteristics, with bandgap energies ranging from 1.392 eV to 1.479 eV. The application of strain systematically influences the electronic properties of the SiC/WS₂ heterojunctions, with the three-layer heterojunction demonstrating heightened sensitivity to strain effects. This three-layer configuration also exhibits enhanced interlayer charge transfer and light absorption capabilities. The superior electronic properties of the SiC/WS₂ heterojunctions underscore their potential utility in electronic and optoelectronic ceramic devices.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115240"},"PeriodicalIF":3.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143844773","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":"Excitations of colored and colorless forms of Meldola's blue dye in aqueous solution: A comparative theoretical analysis","authors":"Ella Tkachenko,&nbsp;Victor Kostjukov","doi":"10.1016/j.comptc.2025.115241","DOIUrl":"10.1016/j.comptc.2025.115241","url":null,"abstract":"<div><div>TD-DFT calculations were performed for the colored (MB⁺) and colorless (МB⁰) forms of the oxazine dye. The nature of excitation of these forms of dye differs significantly: MB⁺ undergoes a local excitation, and МB⁰ has a significant charge transfer. In particular, the dipole moment of MB⁺ upon excitation slightly decreases while for MB⁰, on the contrary, it increases almost fourfold. Spatial structures and their photoinduced distortions also differ: while the MB⁺ chromophore remains flat in both the ground and excited states, MB⁰ has a significant chromophore kink along the N<img>O line in the ground state and becomes flat in the excited state. The mechanisms of solvatochromic behavior of the dye - non-specific and specific interaction with the solvent - were also analyzed.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115241"},"PeriodicalIF":3.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143844770","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 investigation of Al-doped biphenylene as efficient sensor for phosgene detection","authors":"Ali B.M. Ali ,&nbsp;Abdulrahman T. Ahmed ,&nbsp;Maher Ali Rusho ,&nbsp;Suranjana V. Mayani ,&nbsp;Suhas Ballal ,&nbsp;Rishiv Kalia ,&nbsp;Shirin Shomurotova ,&nbsp;V. Kavitha ,&nbsp;Subhashree Ray ,&nbsp;Ahmed M. Naglah","doi":"10.1016/j.comptc.2025.115237","DOIUrl":"10.1016/j.comptc.2025.115237","url":null,"abstract":"<div><div>Phosgene (COCl₂) is a highly toxic gas that poses significant risks to human health and the environment, making its detection and monitoring critically important. In this study, we explored the potential of pristine and aluminum-doped biphenylene (BP) monolayers as sensing materials for phosgene detection using the M062X/6-31G(d,p) level of theory. Aluminum doping was shown to disrupt the uniform electronic density of BP, creating active sites that significantly enhance its reactivity. While phosgene adsorption on pristine BP was weak, with an adsorption energy of −6.93 kcal/mol and minimal changes in electronic properties, thermochemical analysis confirmed that this interaction is non-spontaneous under standard conditions. In contrast, Al-doped BP monolayers (Al1-BP and Al2-BP) exhibited strong phosgene adsorption, with adsorption energies of −20.09 kcal/mol and −21.47 kcal/mol, respectively. Notably, a significant change in the energy gap was observed upon phosgene adsorption on the doped monolayers, and the process was found to be thermodynamically favorable, as indicated by negative free energy values. Natural bond orbital (NBO) analysis revealed that the enhanced sensitivity and reactivity of Al-doped BP arise from donor-acceptor interactions between the lone pair electrons of phosgene oxygen and the Rydberg state of lone pairs from the aluminum dopant. These results demonstrate the promising potential of Al-doped BP monolayers as highly sensitive and efficient materials for phosgene detection.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115237"},"PeriodicalIF":3.0,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143844771","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":"Anisotropic structural response and decomposition behaviors of Hexanitrostilbene under high pressure: Insights from ab initio calculations.","authors":"Hai-Chao Ren,&nbsp;Fan Jiang,&nbsp;Xiao-Yang Wu,&nbsp;Bo Wang,&nbsp;Yi-Ping Wang,&nbsp;Jun Tao","doi":"10.1016/j.comptc.2025.115235","DOIUrl":"10.1016/j.comptc.2025.115235","url":null,"abstract":"<div><div>This study systematically investigates the structural and decomposition behaviors of hexanitrostilbene (HNS) under high pressures (1 atm–10 GPa) via first-principles calculations and experimental validation. Structural analysis reveals anisotropic compression, with the <em>b</em>-axis exhibiting the highest compressibility (reduced to 83.9 % at 10 GPa), while the <em>c</em>-axis anomalously expands at 3 GPa due to differential hydrogen bond network responses. Electronic structure analysis identifies C–NO₂ bond cleavage as the initial decomposition step, with liberated oxygen atoms competing for C<img>H bonds to form NO and OH radicals. High pressure stabilizes C–-NO₂ bonds by strengthening intermolecular hydrogen interactions, delaying decomposition. Infrared spectroscopy confirms the preservation of <em>trans</em>-HNS configuration under compression. These findings elucidate the interplay between mechanical stress and chemical stability in HNS, providing atomistic insights into its shock insensitivity and guiding the design of advanced energetic materials.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115235"},"PeriodicalIF":3.0,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143844772","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":"Exploring the nonlinear optical properties of fluorinated aniline derivatives: A computational and experimental study","authors":"Adnan Ahmed ,&nbsp;Ilham Khan ,&nbsp;Ume Aiman ,&nbsp;Aysha Hina ,&nbsp;Irfan Mushtaq","doi":"10.1016/j.comptc.2025.115224","DOIUrl":"10.1016/j.comptc.2025.115224","url":null,"abstract":"<div><div>This research focuses on the synthesis of derivatives such as 4-(4-<em>tert</em>-butylphenyl)-3-fluoroaniline (<strong>BFPA</strong>), 4-(1,1′-biphenyl-2-fluoroaniline) (<strong>FPA</strong>), 2-fluoro-4-(naphthalen-1-yl)aniline (<strong>FNA</strong>), 2-fluoro-4-(furan-2-yl)aniline (<strong>FFA</strong>), and 4′-amino-3′-fluoro-[1,1′-biphenyl]-4-ol (<strong>AFPO</strong>). Density Functional Theory (DFT) at the B3LYP/6–311 + G (2d,p) level and time-dependent DFT (TD-DFT) were applied to compare experimental spectroscopic data (NMR, FTIR, UV–Vis) with theoretical analysis (FMO, NPA, and NBO). The results showed full agreement between experimental data and DFT conclusions, highlighting how charge delocalization and hyperconjugation contribute to molecular stability. The global reaction characteristics calculated from FMO energy levels revealed that FPPM, with the highest ELUMO-HOMO of 4.91 eV, was the least reactive and most stable. NLO tests confirmed improved properties in the studied compounds, indicating their potential in photoelectric technology.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1249 ","pages":"Article 115224"},"PeriodicalIF":3.0,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143864645","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}