Computational and Theoretical Chemistry最新文献

{"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}

{"title":"Study of electrochemical properties, mechanical properties, and lithium ion diffusion of Ni and N co- doped LiFePO4 based on first principles","authors":"Xinyang Zhao,&nbsp;Fazhan Wang,&nbsp;Kai Jiang,&nbsp;Yumeng Cai,&nbsp;Xiaopeng Li,&nbsp;Haochen Wang,&nbsp;Haizhou Zhang,&nbsp;Lujia Yu","doi":"10.1016/j.comptc.2025.115236","DOIUrl":"10.1016/j.comptc.2025.115236","url":null,"abstract":"<div><div>This study analyzes the stability, volume change rate, embedding voltage, lithium ion diffusion, and mechanical properties of Ni, N co-doped LiFePO₄ using density functional theory (DFT) calculations. Ni,N doping reduces formation energy to −1.5 eV compared to pristine LiFePO₄, stabilizing the olivine framework during lithiation/de-lithiation. The doping of Ni and N introduces impurity bands, and the band gap before and after doping decreases from 3.71 eV to 1.2 eV, which enhances the electronic conductivity. Meanwhile, the migration barrier is reduced from 0.57 eV to about 0.45 eV and the diffusion coefficient is improved by two orders of magnitude. In addition, nickel doping leads to changes in the local electronic structure, and the reduced electron localization helps the migration of lithium ions. Finally, doping enhances the stiffness, hardness of the material, which further improves its overall performance.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115236"},"PeriodicalIF":3.0,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143829243","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 density functional theory investigation of the adsorption of CH4, CO, CO2, H2, H2O, N2, NH3, NO, and NO2 on Mg20 and Mg19Zn clusters","authors":"Mohsen Doust Mohammadi ,&nbsp;Karwan Wasman Qadir ,&nbsp;Hewa Y. Abdullah","doi":"10.1016/j.comptc.2025.115227","DOIUrl":"10.1016/j.comptc.2025.115227","url":null,"abstract":"<div><div>This study investigates the adsorption mechanisms and electronic properties of small molecules (CH₄, CO, CO₂, H₂, H₂O, N₂, NH₃, NO, and NO₂) on pristine Mg₂₀ and Zn-doped Mg₁₉Zn clusters using advanced computational methods. Density Functional Theory (DFT) calculations with the ωB97XD functional and Def2SVPP basis set were employed to accurately capture dispersion interactions and electronic structure. Cluster geometries were globally optimized using the Artificial Bee Colony algorithm, while Natural Bond Orbital (NBO) analysis and Quantum Theory of Atoms in Molecules (QTAIM) provided insights into charge transfer mechanisms and bonding nature. Non-Covalent Interaction analysis via Reduced Density Gradient (NCI-RDG) and Total Density of States (TDOS) calculations were also performed to examine molecular adsorption effects and Zn doping. The adsorption energy trends revealed significant variation in interaction strengths. Polar and reactive molecules, such as H₂O and NO₂, exhibited the highest adsorption energies, with NO₂ showing the strongest binding at −68.80 kcal·mol⁻¹ (Mg₂₀) and − 72.38 kcal·mol⁻¹ (Mg₁₉Zn). Nonpolar gases like CH₄ and H₂ demonstrated weak interactions, with adsorption energies ranging from −0.85 to −1.82 kcal·mol⁻¹. The Mg₁₉Zn cluster consistently showed higher adsorption energies, particularly for polar molecules, due to Zn's influence on the electronic properties of the cluster. Electronic property analysis at bond critical points (BCPs) using QTAIM indicated that the interaction type and strength were system-dependent, with stronger covalent and ionic interactions for molecules like H₂O, NH₃, NO, and NO₂. The substitution of Mg with Zn in Mg₁₉Zn enhanced the ionic and polar nature of interactions. These findings highlight the role of cluster composition in modulating adsorption behavior and provide key insights for the design of optimized materials for gas sensing and catalysis applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115227"},"PeriodicalIF":3.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143823371","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":"Tuning the electronic and adsorption properties of MoSe2 nanosheets by CuO, NiO and pair CuO-NiO metal oxide doping for efficient sensing of caffeine molecule: A DFT study","authors":"Farag M.A. Altalbawy ,&nbsp;Shaker Al-Hasnaawei ,&nbsp;Prakash Kanjariya ,&nbsp;Anjan Kumar ,&nbsp;Asha Rajiv ,&nbsp;Debasish Shit ,&nbsp;Helen Merina Albert ,&nbsp;Sumit Pokhriyal","doi":"10.1016/j.comptc.2025.115234","DOIUrl":"10.1016/j.comptc.2025.115234","url":null,"abstract":"<div><div>In this work, the structures and electronic properties of CuO and NiO doped MoSe₂ nanosheets are investigated using the density functional theory calculations. The structural stability of these metal oxide doped systems was verified using the binding energy analysis, and thus the CuO doped MoSe₂ nanosheets are selected for adsorption and sensing of caffeine molecules. The adsorption energies, density of states, charge density difference, work functions and band structures were examined for the adsorption systems. Caffeine molecules are initially positioned on the CuO clusters of the CuO-MoSe₂ nanosheets, and after the adsorption, the O and N atoms are strongly adsorbed to the CuO clusters. Based on band structure calculations, CuO and NiO doped MoSe₂ nanosheets exhibited semiconductor property and enhanced conductivity because of band gap reduction. These results provide theoretical basis, which is useful in optimizing and developing novel metal oxide doped MoSe₂ nanosheets as sensors for caffeine detection.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115234"},"PeriodicalIF":3.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143829242","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":"Improved nanocarrier systems based on noble metal (Pd, Pt, ag and au) modified BSe nanosheets for β-lapachone drug delivery","authors":"Farag M.A. Altalbawy ,&nbsp;Shaker Al-Hasnaawei ,&nbsp;Suranjana V. Mayani ,&nbsp;G. Padma Priya ,&nbsp;Abhinav Kumar ,&nbsp;Aditya Kashyap ,&nbsp;V. Kavitha ,&nbsp;Kamal Kant Joshi","doi":"10.1016/j.comptc.2025.115233","DOIUrl":"10.1016/j.comptc.2025.115233","url":null,"abstract":"<div><div>The adsorption behaviors of <em>β</em>-lapachone drug molecules on the noble metal (Pd, Pt, Ag and Au) modified BSe nanosheets were investigated using the first principles method. The Pd, Pt, Ag and Au doped BSe substrates exhibit good geometric stability following their large formation energies. The conductivity has been substantially enhanced for BSe monolayers after the modification of surface by Pt and Au atoms, which are subsequently utilized for adsorption and delivery of drug molecules. The O atoms of the <em>β</em>-lapachone drug are the most favorable adsorption sites for reaction with Pt and Au modified BSe nanosheets. The negative adsorption energies verify the stability of adsorption configurations with optimized structures. The charge density difference, work functions and band structures are analyzed to gain insights into the drug delivery systems. Our theoretical results would provide effective basis for experimental design of <em>β</em>-lapachone drug delivery systems using the noble metal modified BSe nanosheets.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1249 ","pages":"Article 115233"},"PeriodicalIF":3.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143873178","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 calculations of the electronic structure and lattice dynamics of ytterbium (Yb) vacancy color Center in Diamond","authors":"Xin Tan ,&nbsp;Zhengyu Liang ,&nbsp;Jian Wang ,&nbsp;Qiao Yang ,&nbsp;Zhanqing He ,&nbsp;Hui Qi ,&nbsp;Chenglei Yang ,&nbsp;Zhiyu Wang","doi":"10.1016/j.comptc.2025.115226","DOIUrl":"10.1016/j.comptc.2025.115226","url":null,"abstract":"<div><div>Ytterbium (Yb) doping in diamond has shown promising potential in optoelectronic applications, standing out among rare-earth-doped luminescent materials. In this study, first-principles calculations based on density functional theory (DFT) were employed to investigate the defect structure, electronic structure, and lattice dynamics of the Yb vacancy color center in diamond. We accurately predicted the zero-phonon line (ZPL) energy corresponding to a wavelength of 1003 nm, considering spin-orbit coupling (SOC), a first in such studies. Band structure and density of states calculations revealed the significant influence of Yb’s 4f orbital characteristics on the system's structure. Lattice Dynamics analysis identified two local vibrational modes of Yb at 26 THz, providing new insights into the phonon dynamics and photoluminescence mechanism of the Yb vacancy color center. These findings offer theoretical insights for further exploration of Yb-doped diamond's properties and applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115226"},"PeriodicalIF":3.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834728","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":"Electromechanical behavior of dual network polyethylene oxide/polyvinyl alcohol composite hydrogel electrolyte for metal-air battery: A DFT and molecular dynamics approach.","authors":"Nkechi Elizabeth Offia-Kalu ,&nbsp;Bernice Ngwi Abraham ,&nbsp;Joseph Ekhebume Ogbezode ,&nbsp;Vitalis Anye ,&nbsp;Simeon Chukwudozie Nwanonenyi ,&nbsp;Abdulhakeem Bello","doi":"10.1016/j.comptc.2025.115232","DOIUrl":"10.1016/j.comptc.2025.115232","url":null,"abstract":"<div><div>Hydrogel electrolytes for metal-air batteries have recently gained attention. However, absence of well-optimized data on their structure-property relationship at the atomic scale limits their practical application. Density functional theory and molecular dynamics techniques were used to investigate the electronic, energetic, transport, and mechanical properties of polyethylene oxide (PEO)/polyvinyl alcohol (PVA) hydrogel electrolytes. Frontier Molecular Orbitals of the PEO molecular chain exhibited its electron transfer potential, and a negative band gap confirmed its stability. The highest binding energy was 374.7 × 10¹⁰ kcal/mol at 343 K. Greater binding energy of the order 0.6 &gt; 0.8 &gt; 1.0 &gt; 0.4 &gt; 0.2 &gt; 1.2 was achieved with optimal value of 0.6 wt% crosslinker concentration. Mean square displacement of potassium ions (K⁺) remained constant with time while diffusion coefficient exhibited a linear correlation with temperatures. Hydrogel composition had varying effects on elastic moduli. The structure-property correlation of PEO and PVA is extremely beneficial in development of enhanced quasi-solid polymer electrolytes for metal-air batteries.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115232"},"PeriodicalIF":3.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143817102","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":"Possibility of gallium sulfide nanoflakes for detection and adsorption of O2 and H2O: A DFT and thermodynamic perspective","authors":"Jyoti Rai ,&nbsp;Kuldeep Kumar ,&nbsp;Mukesh Kumar Verma ,&nbsp;Munish Sharma","doi":"10.1016/j.comptc.2025.115231","DOIUrl":"10.1016/j.comptc.2025.115231","url":null,"abstract":"<div><div>In this study, environmental oxygen and water interaction-driven electronic and thermodynamic properties of pristine and hydrogenated gallium sulfide nanoflakes (GaS-NF) in armchair (AC) and zigzag (ZZ) configurations have been reported. The hydrogenation increases the interaction between GaS nanoflakes, particularly in the zigzag (ZZ) configuration, and the molecules, suggesting enhanced electronic sensitivity in hydrogenated nanoflakes. The ZZ configuration, particularly in the hydrogenated state, shows pronounced reactivity with O₂, maintaining physisorption, as evidenced by the appearance of a prominent O(2p) peak in the density of states analysis. The oxygen interaction increases the quantum capacitance value up to 250 μF/cm² and 200 μF/cm² in zigzag pristine and hydrogenated nanoflake, respectively. Scanning tunneling microscopy (STM) reveals more pronounced electronic localization at the edges. Thermodynamic analysis indicates high adsorption probabilities for both O₂ and H₂O at low temperatures and pressures, with the ZZ configuration being suitable for oxygen detection and the AC configuration for humidity sensing and water filtration applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115231"},"PeriodicalIF":3.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143823443","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}