Computational and Theoretical Chemistry最新文献

{"title":"Enhanced Corrosion-Inhibition performance of amino Gossypol: A comprehensive theoretical study","authors":"Khasan Berdimuradov ,&nbsp;Elyor Berdimurodov ,&nbsp;Brahim El Ibrahimi ,&nbsp;Muslum Demir ,&nbsp;Suleyman Gokhan Colak ,&nbsp;Burak TÜZÜN ,&nbsp;Mavjuda Rakhmatullaeva ,&nbsp;Muhabbat Diyorova ,&nbsp;Dilshod Axtamov ,&nbsp;Qaxramon Husenov","doi":"10.1016/j.comptc.2024.114920","DOIUrl":"10.1016/j.comptc.2024.114920","url":null,"abstract":"<div><div>This study highlights the potential of amino gossypol as a green corrosion inhibitor. Comprehensive DFT calculations reveal that the electronic properties of amino gossypol, including HOMO and LUMO values, which indicate its strong electron transfer capacity and effective adsorption on steel surfaces. DFT research demonstrates a good electron transfer capacity with HOMO and LUMO values of −5.1103 eV and −0.947 eV, respectively. The study employs (molecular dynamics (MD) and Monte Carlo (MC)) simulations to investigate the interaction dynamics of amino gossypol with steel, demonstrating robust adsorption energy and the formation of a stable protective layer. The inhibitor’s adsorption energy of −65.108 Kcal/mol shows robust and spontaneous adhesion to steel, increased by its optimized molecular structure and physisorption and chemisorption methods. The substantial polarizability (<span><math><msubsup><mi>γ</mi><mrow><mi>I</mi><mi>n</mi><mi>h</mi></mrow><mrow><mi>D</mi><mi>F</mi><mi>T</mi></mrow></msubsup></math></span> = 452.31) and specific charge distribution, with significant negative charges on oxygen atoms, facilitate efficient corrosion inhibition. Theoretical results, including reactivity indices such as chemical softness (0.4804) and electrophilicity index (2.2031), establish a strong platform for future practical investigation and possible commercial use of amino gossypol. MD simulations confirm the formation of a stable and persistent protective layer on Fe(110) surfaces. Amino gossypol is presented as an environmentally friendly and sustainable corrosion inhibitor, aligning with the growing demand for green industrial solutions. The theoretical and computational analyses predict significant corrosion inhibition performance of amino gossypol, supported by its optimized molecular structure and strong binding affinity to steel.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114920"},"PeriodicalIF":3.0,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529114","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":"Deeply insight into the inhibition mechanism of SO2 on mercury oxidation over Mn/CNT: A DFT study","authors":"Bo Zhao ,&nbsp;Xi Sun ,&nbsp;Linbo Qin ,&nbsp;Qiang Zhang ,&nbsp;Zeli Wang ,&nbsp;Wangsheng Chen ,&nbsp;Jun Han","doi":"10.1016/j.comptc.2024.114918","DOIUrl":"10.1016/j.comptc.2024.114918","url":null,"abstract":"<div><div>Mn/CNT is a kind of low temperature catalyst, which can effectively remove elemental mercury from flue gas at low temperature, but its mercury removal ability was significantly inhibited by SO₂. In this work, the inhibition mechanism of SO₂ was investigated by first-principle calculation based on density functional theory. Three different surfaces of Mn/CNT were constructed: MnO/CNT, MnO₂/CNT and Mn₂O₃/CNT, and the adsorption of Hg⁰ and SO₂ on these three surfaces were studied. It suggests that adsorption energy of Hg⁰ on MnO/CNT is the highest, which is −2.42 eV. Combined with the electron partial density of states (PDOS) after adsorption, SO₂ can compete with Hg⁰ for the same Mn active site on the catalyst surface during the adsorption process, and the adsorption capacity of Hg⁰ is weaker than that of SO₂. Oxidation path of Hg⁰ to HgO on the surface of Mn/CNT indicates that the generation of HgO needs to cross at least two energy barriers, with energies of 0.552 eV and 1.25 eV, respectively. However, when Hg⁰ was oxidized to HgO and adsorbed on the surface of Mn/CNT, SO₂ could reduce it to Hg⁰ again, generating SO₃ to block elemental mercury oxidation.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114918"},"PeriodicalIF":3.0,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142446161","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":"NLOphoric unsymmetrically substituted D-π-A benzodifuranone dyes: Density functional theory, time dependent-density functional theory, and non-linear optical studies","authors":"Aishwarya A. Zambare,&nbsp;Mayuri S. Bagal,&nbsp;Suryapratap J. Sharma,&nbsp;Nagaiyan Sekar","doi":"10.1016/j.comptc.2024.114919","DOIUrl":"10.1016/j.comptc.2024.114919","url":null,"abstract":"<div><div>The linear and non-linear optical properties of thirty-five unsymmetrically substituted compounds are studied using density functional theory and time-dependent density functional theory methods (B3LYP/6311++G(d,p), CAM-B3LYP/6311++G(d,p) and M06-2X/6311++G(d,p)). A comparable set of functionals is also used to investigate vertical excitation. It is observed that the inclusion of the nitrogen-substituted electron-donating group along with the electron-withdrawing group led to more red-shifted absorption maxima and exhibited an excellent (non-linear optical) NLO response. The geometrical framework, dipole moment, and other descriptors, HOMO-LUMO energy gaps, linear polarizability, first-order and second-order hyperpolarizability are calculated to investigate the effect of different electron donating and accepting substituents on the NLO properties of benzodifuranone chromophores. In cases where nitrogen substituents are added, the electron density is more widely spread throughout the donor in HOMO and more displaced to the acceptor in LUMO. The computed first-order and second-order hyperpolarizability values and decreasing HOMO-LUMO energy gaps in disubstituted nitrogen-containing compounds show that <strong>1a-1e, 4a-4e, 5a-5e</strong> are promising candidates in all functionals for better NLO properties.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114919"},"PeriodicalIF":3.0,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142446162","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":"Effect of doping with M (M=Al, Pd, Ti, Ge) on the electronic structure and hydrogen diffusion behavior of amorphous silicon","authors":"Zongkun Bian,&nbsp;Qiankun Zhang,&nbsp;Haimin Zhang,&nbsp;Fuling Tang,&nbsp;Zhewen Ma,&nbsp;Xuan Lan,&nbsp;Yongchun Luo","doi":"10.1016/j.comptc.2024.114915","DOIUrl":"10.1016/j.comptc.2024.114915","url":null,"abstract":"<div><div>Amorphous silicon (a-Si) models doped with Pd, Ge, Al, and Ti (a-Si/M) at three different doping ratios are generated using <em>Ab initio</em> Molecular Dynamics (AIMD) high-temperature annealing, followed by analysis utilizing first-principles method. The electronic structure calculations reveal strong interactions between Al, Ge and Si, while interaction between Pd, Ti and Si are relatively weak. Moderate doping of Pd and Ti can reconstruct the a-Si surface, reduce the adsorption energy of H on the surface, and increase the Si-Si atomic gap. This will greatly reduce the energy barrier for H to diffuse on the surface and to the subsurface.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114915"},"PeriodicalIF":3.0,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554745","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":"Magnetic and electronic properties of 1D hybrid nanoobjects composed of alternating polycyclic hydrocarbon regions and double carbon chains","authors":"Irina V. Lebedeva ,&nbsp;Sergey A. Vyrko ,&nbsp;Alexander S. Sinitsa ,&nbsp;Sergey V. Ratkevich ,&nbsp;Andrey M. Popov ,&nbsp;Andrey A. Knizhnik ,&nbsp;Nikolai A. Poklonski ,&nbsp;Yurii E. Lozovik","doi":"10.1016/j.comptc.2024.114913","DOIUrl":"10.1016/j.comptc.2024.114913","url":null,"abstract":"<div><div>It has been proposed recently that 1D hybrid nanoobjects consisting of alternating double carbon chains and polycyclic carbon regions can be obtained from graphene nanoribbons of alternating width by electron irradiation. Here, based on density functional theory calculations, we show that magnetic and electronic properties of such nanoobjects can be changed dramatically by modifying the chain length and edge structure of polycyclic regions and this opens wide possibilities for spintronic applications. Nanoobjects composed of polycyclic regions with dangling bonds and even chains are found to behave as magnetic semiconductors that can generate spin-polarized currents. Band gaps of nanoobjects with odd chains change considerably upon switching between magnetic states making them promising for magnetic tunnel junctions. We also demonstrate that use of a hybrid exchange–correlation functional is important to properly describe stability of magnetic states, band gaps and synergistic effects of nanoobject components leading, for example, to magnetism in even chains.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114913"},"PeriodicalIF":3.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529643","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":"Transition metals tailoring of phosphorus-doped gallium nitride nanotubes as sensors for N-butenyl homoserine lactone (BHL): A computational study","authors":"Bassey O. Ekpong ,&nbsp;Hewa Y. Abdullah ,&nbsp;Emmanuel Emmanuel ,&nbsp;Innocent Benjamin ,&nbsp;Daniel C. Agurokpon","doi":"10.1016/j.comptc.2024.114914","DOIUrl":"10.1016/j.comptc.2024.114914","url":null,"abstract":"<div><div>This investigation is focused on the impact of transition metals (Ag, Au, and Cu) encapsulations of phosphorus-doped gallium nitride nanotubes (P@GaNNTs) to achieve precise detection and sensing of <em>N</em>-Butenyl homoserine lactone (BHL), which is a biomarker for urinary tract infection, within the framework of density functional theory (DFT) computation at the B3LYP-D3(BJ)/def2SVP method. Adsorption studies unveil the adsorption energies for BHL detection across the systems, with BHL_Cu_P@GaNNT displaying the most favorable adsorption energy of −1.79247 eV and BSSE correction (−1.7685 eV). Additionally, sensor mechanisms are elucidated through Fermi energy level (E_FL) calculations, revealing distinct values of 4.748, 4.242, 5.052, and 3.864 for BHL_Ag_P@GaNNT, BHL_Au_P@GaNNT, BHL_Cu_P@GaNNT, and BHL_P@GaNNT, respectively. These values signify variances in charge transfer dynamics upon BHL interaction. In essence, this study lays the foundation for the development of highly efficient biosensors with exceptional biomarker detection capabilities, particularly in the context of urinary tract infections (UTIs). It opens new avenues in the realm of biosensing technology, promising innovative solutions for healthcare and diagnostics.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114914"},"PeriodicalIF":3.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142438330","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":"Investigation of the structural, electronic, magnetic, and optical properties of the double perovskite oxide semiconductor La2NiMnO6: Ab initio calculations by using GGA-PBE and GGA + mBJ approximations","authors":"M. Jerrari,&nbsp;R. Masrour,&nbsp;T. Sahdane","doi":"10.1016/j.comptc.2024.114912","DOIUrl":"10.1016/j.comptc.2024.114912","url":null,"abstract":"<div><div>In this paper, we examined the La₂NiMnO₆ double perovskite oxide semiconductor materials, our treatment included the structural, electronic, magnetic, and optical characteristics by utilizing the density functional theory, which was performed in the Wien2k software. The exchange–correlation potential was carried out in combination with the GGA-PBE (Perdew Burke Ernzerhof Generalized Gradient Approximation), and GGA + mBJ (modified Becke and Johnson) was used for the exchange–correlation potentials. The results suggest that the compound La₂NiMnO₆ exhibits in a ferrimagnetic state. It was also found that the stable ground state of the compound is ferrimagnetic. The results demonstrate that La₂NiMnO₆ has a band gap whose spin-up value is 0 eV and spin-down (<em>dn</em>) value is 2.86 eV (GGA-PBE), with up values is 0 eV and dn value being of 3 eV (GGA + mBJ). We also explored different optical properties, among them electron energy loss, absorption coefficient, real and imaginary dielectric tensor, and real and imaginary optical conductivity.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114912"},"PeriodicalIF":3.0,"publicationDate":"2024-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142422843","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":"Effects of N, O, S on generalized stacking fault energies and dislocation movements in γ-Ni and γ′-Ni3Al","authors":"Xinyue Zhang,&nbsp;Xiaohua Min,&nbsp;Chao Lu","doi":"10.1016/j.comptc.2024.114909","DOIUrl":"10.1016/j.comptc.2024.114909","url":null,"abstract":"<div><div>The effects of interstitial atoms (N, O and S) on generalized stacking fault energies in the γ-Ni and γ′-Ni₃Al were systematically elucidated by first-principles calculations. N, O and S atoms had the preference for octahedral interstitial sites in γ phase. N and S atoms had the preference for octahedral interstitial site with 6Ni atoms in γ′ phase, while O atom had the preference for octahedral interstitial site with 2Al4Ni atoms. With the addition of adopted atoms, the intrinsic stacking fault energy in γ phase was decreased and the anti-phase boundary energy in γ′ phase was increased, which were attributed to the charge redistribution between the adopted atoms and neighbouring Ni atoms. The addition of N, S, especially O, hindered the extended dislocation movement and enhanced its formation probability. The addition of O and S atoms significantly enhanced the formation probability of Kear-Wilsdorf dislocation lock in γ′ phase, while the addition of N slightly reduced it.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114909"},"PeriodicalIF":3.0,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142442406","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 permeation and selective separation of hydrogen isotopes through fullerene nanocages (X12Y12): A DFT insights","authors":"Misbah Asif ,&nbsp;Imene Bayach ,&nbsp;Nadeem S. Sheikh ,&nbsp;Khurshid Ayub","doi":"10.1016/j.comptc.2024.114910","DOIUrl":"10.1016/j.comptc.2024.114910","url":null,"abstract":"<div><div>To resolve the problem of mobile electrolytes for the permeation of hydrogen isotopes in fuel cells, we have studied herein heteronuclear fullerene nanocages (Al₁₂N₁₂, Al₁₂P₁₂, B₁₂N₁₂, and B₁₂P₁₂) for the separation and permeation of hydrogen isotopes. The separation and permeation of fullerene nanocages for hydrogen isotopes are studied at ωB97XD functional of DFT along with 6–31g (d,p) pople basis set. Zero-point energy (ZPE) is calculated for Protium (H⁺) and its heavier isotopes including deuterium (D⁺) and tritium (T⁺). The Arrhenius equation is employed to calculate the selectivity of protium to deuterium (H⁺/D⁺) and deuterium to tritium (H⁺/T⁺) isotopes. The selectivity is calculated by using the zero-point energy difference (ZPE) of protium (H⁺) to its heavier isotopes. The proposed fullerene nanocages estimated better selectivity for proton isotopes. The phosphide-based nanocages (Al₁₂P₁₂, B₁₂P₁₂) provide superior selectivity values of H⁺/D⁺ and H⁺/T⁺ compared to nitrogen-based nanocages (Al₁₂N₁₂, B₁₂N₁₂). This study provides insights into separation pathways for proton isotopes through nanocages for many industrial applications in the energy sector.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114910"},"PeriodicalIF":3.0,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142422924","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":"Effect of nitrogen- and oxygen-containing functional groups on adsorption of styrene by activated carbon: A theoretical study by density functional theory","authors":"Yihuan Zhou,&nbsp;Qiang Xie,&nbsp;Hongyang Zhou,&nbsp;Shimei Gu,&nbsp;Dingcheng Liang,&nbsp;Jinchang Liu","doi":"10.1016/j.comptc.2024.114896","DOIUrl":"10.1016/j.comptc.2024.114896","url":null,"abstract":"<div><div>Activated carbon adsorption is one of the mainstream technologies for controlling VOCs emissions such as styrene, with surface functional groups significantly influencing its adsorption capacity. The adsorption mechanism of styrene on functionalized AC was studied using DFT calculations. Results show that nitrogen and oxygen doping altered the local electrostatic potential of AC, reduced the average LOLIPOP index of the internal ring, and enhanced styrene adsorption to varying degrees. AC with hydroxyl and pyrrolic groups significantly improved styrene adsorption (Ead = -13.76, -12.86 kcal/mol). Styrene adsorption on AC is a physisorption process, primarily dominated by π-π stacking, with dispersion interactions as the main contributor (61–70 %). In addition to π-π stacking, weak hydrogen bonds between styrene and AC functionalized with hydroxyl, amino, and pyrrolic N groups further enhance the adsorption capacity. Enhancing the synergistic effect of hydrogen bonding and π-π stacking is key to significantly improving adsorption capacity.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114896"},"PeriodicalIF":3.0,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142422932","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}