Pub Date : 2024-10-05DOI: 10.1016/j.comptc.2024.114909
Xinyue Zhang, Xiaohua Min, Chao Lu
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.
第一原理计算系统地阐明了间隙原子（N、O 和 S）对γ-Ni 和 γ′-Ni3Al 中广义堆积断层能的影响。在γ相中，N、O和S原子偏爱八面体间隙位点。在γ′相中，N 原子和 S 原子偏好与 6Ni 原子的八面体间隙位点，而 O 原子偏好与 2Al4Ni 原子的八面体间隙位点。随着被接纳原子的加入，γ 相的本征堆积断层能降低，γ′ 相的反相边界能增加，这归因于被接纳原子与相邻镍原子之间的电荷再分配。N、S，尤其是 O 原子的加入阻碍了扩展位错的运动，提高了其形成概率。O 原子和 S 原子的加入大大提高了γ′相中 Kear-Wilsdorf 位错锁的形成概率，而 N 原子的加入则略微降低了这一概率。
{"title":"Effects of N, O, S on generalized stacking fault energies and dislocation movements in γ-Ni and γ′-Ni3Al","authors":"Xinyue Zhang, Xiaohua Min, 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′-Ni<sub>3</sub>Al 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}
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.
{"title":"Proton permeation and selective separation of hydrogen isotopes through fullerene nanocages (X12Y12): A DFT insights","authors":"Misbah Asif , Imene Bayach , Nadeem S. Sheikh , 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 (Al<sub>12</sub>N<sub>12</sub>, Al<sub>12</sub>P<sub>12</sub>, B<sub>12</sub>N<sub>12</sub>, and B<sub>12</sub>P<sub>12</sub>) 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<sup>+</sup>) and its heavier isotopes including deuterium (D<sup>+</sup>) and tritium (T<sup>+</sup>). The Arrhenius equation is employed to calculate the selectivity of protium to deuterium (H<sup>+</sup>/D<sup>+</sup>) and deuterium to tritium (H<sup>+</sup>/T<sup>+</sup>) isotopes. The selectivity is calculated by using the zero-point energy difference (ZPE) of protium (H<sup>+</sup>) to its heavier isotopes. The proposed fullerene nanocages estimated better selectivity for proton isotopes. The phosphide-based nanocages (Al<sub>12</sub>P<sub>12</sub>, B<sub>12</sub>P<sub>12</sub>) provide superior selectivity values of H<sup>+</sup>/D<sup>+</sup> and H<sup>+</sup>/T<sup>+</sup> compared to nitrogen-based nanocages (Al<sub>12</sub>N<sub>12</sub>, B<sub>12</sub>N<sub>12</sub>). 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}
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.
活性炭吸附是控制苯乙烯等挥发性有机化合物排放的主流技术之一，其表面官能团对吸附能力有很大影响。本文利用 DFT 计算研究了苯乙烯在功能化活性炭上的吸附机理。结果表明，氮和氧的掺杂改变了 AC 的局部静电位，降低了内环的平均 LOLIPOP 指数，在不同程度上增强了苯乙烯的吸附能力。带有羟基和吡咯烷基团的 AC 能明显改善苯乙烯的吸附（Ead = -13.76, -12.86 kcal/mol）。苯乙烯在 AC 上的吸附是一个物理吸附过程，主要由 π-π 堆叠作用主导，而分散相互作用是主要的吸附作用（61-70%）。除了 π-π 堆叠作用外，苯乙烯与羟基、氨基和吡咯烷 N 基团官能化的 AC 之间的弱氢键也进一步增强了吸附能力。增强氢键和 π-π 堆叠的协同效应是显著提高吸附容量的关键。
{"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, Qiang Xie, Hongyang Zhou, Shimei Gu, Dingcheng Liang, 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}
Pub Date : 2024-10-03DOI: 10.1016/j.comptc.2024.114908
R. Abhijith , Riya Datta , S. Sakthivel , Jamal M. Khaled , S. Muthu
This work contains computational investigations of a benzimidazole derivative consisting of density functional theory, electronic structure and biological evaluation of a benzimidazole derivative. Density functional theory evaluation were conducted, starting from geometry optimisation, followed by the molecular electrostatic potential, spectral analyses, polarizability studies and thermodynamic analyses via the frequency calculations. Solvent frontier molecular orbital analyses, impact on the properties of the molecule were modelled with the IEFPCM model of solvation. Topological analyses helped to ascertain the molecule’s electronic structure. Biological assessment included pharmacokinetic property evaluation and molecular docking. Pharmacokinetic descriptors were generated using online tools and the molecule was assessed for its efficacy as a drug molecule by comparing with the rules concerning drug-likeness and analysing the descriptors relating to absorption, distribution, metabolism, excretion and toxicity of the molecule. Docking of the molecule with the two targets, 7D3E and 3A1F, yielded a good binding energy of −7.39 and −5.81 kcal/mol respectively.
{"title":"Computational investigation into the structure, effect of band gap energies, charge transfer, reactivity, thermal energies and NADPH inhibitory activity of a benzimidazole derivative","authors":"R. Abhijith , Riya Datta , S. Sakthivel , Jamal M. Khaled , S. Muthu","doi":"10.1016/j.comptc.2024.114908","DOIUrl":"10.1016/j.comptc.2024.114908","url":null,"abstract":"<div><div>This work contains computational investigations of a benzimidazole derivative consisting of density functional theory, electronic structure and biological evaluation of a benzimidazole derivative. Density functional theory evaluation were conducted, starting from geometry optimisation, followed by the molecular electrostatic potential, spectral analyses, polarizability studies and thermodynamic analyses via the frequency calculations. Solvent frontier molecular orbital analyses, impact on the properties of the molecule were modelled with the IEFPCM model of solvation. Topological analyses helped to ascertain the molecule’s electronic structure. Biological assessment included pharmacokinetic property evaluation and molecular docking. Pharmacokinetic descriptors were generated using online tools and the molecule was assessed for its efficacy as a drug molecule by comparing with the rules concerning drug-likeness and analysing the descriptors relating to absorption, distribution, metabolism, excretion and toxicity of the molecule. Docking of the molecule with the two targets, 7D3E and 3A1F, yielded a good binding energy of −7.39 and −5.81 kcal/mol respectively.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114908"},"PeriodicalIF":3.0,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142422927","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}
The current study explores the trapping of harmful gases using porous organic cage CC1, a covalently bound imine cage with accessible voids. Using WB97XD/6-311G(d, p) theory level, the research computes CC1 and its complexes with pollutants like H2S, SF6, SF4, SOCl2, and SO2. DOS and FMO analyses are performed at DFT/ B3LYP/6-311G(d, p) theoretical level. Interaction energy, NCI, QTAIM, EDD, NBO, charge dissociation, FMO, DOS, and MEP studies provide a detailed insight into the analytes@CC1 complexation. Interaction energies (−4.49 to −0.34 eV) show strong trapping of SOCl2 and SF4 while, slight trapping of H2S within the cavity of CC1. Thermodynamic parameters confirm these findings. Analyses (NCI, QTAIM) indicate strong non-covalent interactions, especially for SOCl2 and SF4. NBO analysis reveals charge transfer from analytes to the cage, except for H2S. EDD analysis is also implemented to verify NBO charge transfer. This study highlights CC1′s peculiar trapping behaviour for the considered analytes.
{"title":"Peculiar trapping behavior of porous organic nanocage CC1 towards H2S, SF6, SF4, SOCl2 and SO2; A DFT Perspective","authors":"Sadia Rani , Riaz Hussain , Samina Aslam , Sehrish Sarfaraz , Ajaz Hussain , Muhammad Durair Sajjad Haider , Mirza Arfan Yawer , Muhammad Imran , Khurshid Ayub","doi":"10.1016/j.comptc.2024.114898","DOIUrl":"10.1016/j.comptc.2024.114898","url":null,"abstract":"<div><div>The current study explores the trapping of harmful gases using porous organic cage CC1, a covalently bound imine cage with accessible voids. Using WB97XD/6-311G(d, p) theory level, the research computes CC1 and its complexes with pollutants like H<sub>2</sub>S, SF<sub>6</sub>, SF<sub>4</sub>, SOCl<sub>2</sub>, and SO<sub>2</sub>. DOS and FMO analyses are performed at DFT/ B3LYP/6-311G(d, p) theoretical level. Interaction energy, NCI, QTAIM, EDD, NBO, charge dissociation, FMO, DOS, and MEP studies provide a detailed insight into the analytes@CC1 complexation. Interaction energies (−4.49 to −0.34 eV) show strong trapping of SOCl<sub>2</sub> and SF<sub>4</sub> while, slight trapping of H<sub>2</sub>S within the cavity of CC1. Thermodynamic parameters confirm these findings. Analyses (NCI, QTAIM) indicate strong non-covalent interactions, especially for SOCl<sub>2</sub> and SF<sub>4</sub>. NBO analysis reveals charge transfer from analytes to the cage, except for H<sub>2</sub>S. EDD analysis is also implemented to verify NBO charge transfer. This study highlights CC1′s peculiar trapping behaviour for the considered analytes.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114898"},"PeriodicalIF":3.0,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142422925","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}
Pub Date : 2024-10-03DOI: 10.1016/j.comptc.2024.114911
Shu Zijing
Density functional theory (DFT) calculations are used to thoroughly examine the reactivity and electronic sensitivity of pristine and BN-doped graphyne (BNG) toward nitrogen mustard (NM). Graphyne’s electrical conductivity is unaffected by the weak adsorption of NM, which occurs via the Cl atom on the material with an adsorption energy of roughly −3.1 kcal.mol−1. In addition to decreasing graphyne’s reactivity and work function, substituting isoelectronic BN linkages for CC linkages enhances the HOMO-LUMO energy gap (Eg). BNG’s electrical conductivity increases when Eg drops from 2.99 to 1.82 eV due to the adsorption of NM. Additionally, a significant change in BNG’s work function results in a variation in the field electron emission current. Lastly, it is anticipated that the desorption of NM from the BNG surface will take a brief recovery time of roughly 0.05 s at room temperature. It has also been demonstrated that NM concentration affects changes in electrical conductivity. The findings also suggest that BNG could be a promising NM sensor.
{"title":"Evaluate the potential adsorption of graphynes (perfect and doped) for nitrogen mustard gas: A first principles study","authors":"Shu Zijing","doi":"10.1016/j.comptc.2024.114911","DOIUrl":"10.1016/j.comptc.2024.114911","url":null,"abstract":"<div><div>Density functional theory (DFT) calculations are used to thoroughly examine the reactivity and electronic sensitivity of pristine and BN-doped graphyne (BNG) toward nitrogen mustard (NM). Graphyne’s electrical conductivity is unaffected by the weak adsorption of NM, which occurs via the Cl atom on the material with an adsorption energy of roughly −3.1 kcal.mol<sup>−1</sup>. In addition to decreasing graphyne’s reactivity and work function, substituting isoelectronic <img>B<img>N<img> linkages for <img>C<img>C<img> linkages enhances the HOMO-LUMO energy gap (Eg). BNG’s electrical conductivity increases when Eg drops from 2.99 to 1.82 eV due to the adsorption of NM. Additionally, a significant change in BNG’s work function results in a variation in the field electron emission current. Lastly, it is anticipated that the desorption of NM from the BNG surface will take a brief recovery time of roughly 0.05 s at room temperature. It has also been demonstrated that NM concentration affects changes in electrical conductivity. The findings also suggest that BNG could be a promising NM sensor.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114911"},"PeriodicalIF":3.0,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529645","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}
At present, some progress has been made in the study of Hf doping on the conductivity. However, few studies on the effects of Hf doping, and O vacancy and interstitial H co-existence on photoelectric properties of β-Ga2O3. O vacancy and interstitial H will inevitably exist during the preparation of β-Ga2O3. Given these problems, the effects of Hf doping, O vacancy and interstitial H co-existence on photoelectric properties of β-Ga2O3 were studied using first-principles calculations. Results show that doping and defects affect the photoelectric properties of β-Ga2O3 to some extent. With increased Hf doping concentration, the bandgap of the system decreases gradually, the absorption spectrum in the deep ultraviolet region red shifts, the carrier activity and carrier lifetime are enhanced. The mobility and conductivity of the system also increase with increased doping concentration. The Hf doping and interstitial H can effectively improve the conductivity of the system. In summary, Hf can be used as a powerful candidate material for designing and preparing β-Ga2O3 optoelectronic devices.
目前，掺杂 Hf 对导电性的研究已取得了一些进展。然而，有关掺杂 Hf 以及 O 空位和间隙 H 共存对 β-Ga2O3 光电特性影响的研究却很少。在制备 β-Ga2O3 的过程中，O 空位和间隙 H 不可避免地会存在。鉴于这些问题，我们利用第一性原理计算研究了 Hf 掺杂、O 空位和间隙 H 共存对 β-Ga2O3 光电特性的影响。结果表明，掺杂和缺陷在一定程度上影响了 β-Ga2O3 的光电特性。随着 Hf 掺杂浓度的增加，体系的带隙逐渐减小，深紫外区的吸收光谱发生红移，载流子活度和载流子寿命增强。系统的迁移率和电导率也随着掺杂浓度的增加而增加。掺杂 Hf 和间隙 H 能有效提高体系的导电性。总之，Hf 可作为设计和制备 β-Ga2O3 光电器件的有力候选材料。
{"title":"First-principle study of the effect of Hf doping and VO-Hi co-existence on absorption spectrum, conductivity and carrier activity of β-Ga2O3","authors":"Ding-du Chen, Shu-min Wen, Xia Liu, Wei Wang, Er-jun Zhao","doi":"10.1016/j.comptc.2024.114906","DOIUrl":"10.1016/j.comptc.2024.114906","url":null,"abstract":"<div><div>At present, some progress has been made in the study of Hf doping on the conductivity. However, few studies on the effects of Hf doping, and O vacancy and interstitial H co-existence on photoelectric properties of β-Ga<sub>2</sub>O<sub>3</sub>. O vacancy and interstitial H will inevitably exist during the preparation of β-Ga<sub>2</sub>O<sub>3.</sub> Given these problems, the effects of Hf doping, O vacancy and interstitial H co-existence on photoelectric properties of β-Ga<sub>2</sub>O<sub>3</sub> were studied using first-principles calculations. Results show that doping and defects affect the photoelectric properties of β-Ga<sub>2</sub>O<sub>3</sub> to some extent. With increased Hf doping concentration, the bandgap of the system decreases gradually, the absorption spectrum in the deep ultraviolet region red shifts, the carrier activity and carrier lifetime are enhanced. The mobility and conductivity of the system also increase with increased doping concentration. The Hf doping and interstitial H can effectively improve the conductivity of the system. In summary, Hf can be used as a powerful candidate material for designing and preparing β-Ga<sub>2</sub>O<sub>3</sub> optoelectronic devices.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114906"},"PeriodicalIF":3.0,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142422926","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}
Pub Date : 2024-10-02DOI: 10.1016/j.comptc.2024.114907
Ting-Ting Liu , Yan Yan , Yu Yang, Na Hou
Nonlinear optical response of four [22]smaragdyrin-BF2 (S)-NiII porphyrin (P) fused hybrids were explored by using DFT at CAM-B3LYP/6–31 + G(d)/SDD level of theory. We choose two types of hybrids, SP and PSP fused hybrids, for our study. Calculations indicate that these fused hybrids might be promising candidates for NLO materials based on considerable static and dynamic hyper-Rayleigh scattering (HRS) hyperpolarizability. The PSP fused hybrids possess larger first hyperpolarizabilities values compared to SP hybrids. Further analysis of hyperpolarizability density reveals the nature of the large first hyperpolarizability of the PSP fused hybrids. For all compounds, HRS hyperpolarizability at λ = 1907 nm is higher than the static value. After the interpretation of dipolar and octupolar character of βHRS, these hybrids show the high dipolar character.
{"title":"A DFT study of the second-order nonlinear optical properties of [22]smaragdyrin-BF2-NiII porphyrin fused hybrids","authors":"Ting-Ting Liu , Yan Yan , Yu Yang, Na Hou","doi":"10.1016/j.comptc.2024.114907","DOIUrl":"10.1016/j.comptc.2024.114907","url":null,"abstract":"<div><div>Nonlinear optical response of four [22]smaragdyrin-BF<sub>2</sub> (<strong>S</strong>)-Ni<sup>II</sup> porphyrin (<strong>P</strong>) fused hybrids were explored by using DFT at CAM-B3LYP/6–31 + G(d)/SDD level of theory. We choose two types of hybrids, <strong>S</strong><img><strong>P</strong> and <strong>P</strong><img><strong>S</strong><img><strong>P</strong> fused hybrids, for our study. Calculations indicate that these fused hybrids might be promising candidates for NLO materials based on considerable static and dynamic hyper-Rayleigh scattering (HRS) hyperpolarizability. The <strong>P</strong><img><strong>S</strong><img><strong>P</strong> fused hybrids possess larger first hyperpolarizabilities values compared to <strong>S</strong><img><strong>P</strong> hybrids. Further analysis of hyperpolarizability density reveals the nature of the large first hyperpolarizability of the <strong>P</strong><img><strong>S</strong><img><strong>P</strong> fused hybrids. For all compounds, HRS hyperpolarizability at λ = 1907 nm is higher than the static value. After the interpretation of dipolar and octupolar character of <em>β</em><sub>HRS</sub>, these hybrids show the high dipolar character.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114907"},"PeriodicalIF":3.0,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142422930","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}
Pub Date : 2024-10-02DOI: 10.1016/j.comptc.2024.114905
Yonggang Xiong , Tao Yao , Fang Xie
Heptafluoro-isobutyronitrile (C4F7N) is a novel environmentally friendly insulating and arc extinguishing gas utilized as a replacement for SF6 in gas insulated equipment (GIE). Nevertheless, the potentially hazardous decomposition byproducts of C4F7N resulting from sudden equipment failure may jeopardize the normal operation of GIE and the physical well-being of the operator. In this paper, using the first principles study the adsorption behavior of four common C4F7N decomposition gases (CF4, COF2, CF3CN, C2F5CN) on PdSe2 monolayer, and explore the adsorption mechanism of PdSe2 monolayer on C4F7N decomposition gas. The results show that the PdSe2 monolayer interacts with the four decomposition gases by physical adsorption mechanism, in which the PdSe2 monolayer causes the largest change in electronic properties and maximum work function (0.15 eV) near the Fermi level before and after adsorption of C2F5CN, indicating a strong interaction between C2F5CN and PdSe2 monolayer. The sensitivity of PdSe2 monolayer to C2F5CN was up to 68.61 %. Therefore, PdSe2 monolayer has the potential of selective detection of C2F5CN gas sensing materials, and the findings in this paper provide theoretical guidance for the development of PdSe2 monolayer gas sensing sensors for monitoring C4F7N insulation equipment.
{"title":"Adsorption of eco-friendly insulating gas C4F7N on PdSe2 monolayer surface: A first-principles study","authors":"Yonggang Xiong , Tao Yao , Fang Xie","doi":"10.1016/j.comptc.2024.114905","DOIUrl":"10.1016/j.comptc.2024.114905","url":null,"abstract":"<div><div>Heptafluoro-isobutyronitrile (C<sub>4</sub>F<sub>7</sub>N) is a novel environmentally friendly insulating and arc extinguishing gas utilized as a replacement for SF<sub>6</sub> in gas insulated equipment (GIE). Nevertheless, the potentially hazardous decomposition byproducts of C<sub>4</sub>F<sub>7</sub>N resulting from sudden equipment failure may jeopardize the normal operation of GIE and the physical well-being of the operator. In this paper, using the first principles study the adsorption behavior of four common C<sub>4</sub>F<sub>7</sub>N decomposition gases (CF<sub>4</sub>, COF<sub>2</sub>, CF<sub>3</sub>CN, C<sub>2</sub>F<sub>5</sub>CN) on PdSe<sub>2</sub> monolayer, and explore the adsorption mechanism of PdSe<sub>2</sub> monolayer on C<sub>4</sub>F<sub>7</sub>N decomposition gas. The results show that the PdSe<sub>2</sub> monolayer interacts with the four decomposition gases by physical adsorption mechanism, in which the PdSe<sub>2</sub> monolayer causes the largest change in electronic properties and maximum work function (0.15 eV) near the Fermi level before and after adsorption of C<sub>2</sub>F<sub>5</sub>CN, indicating a strong interaction between C<sub>2</sub>F<sub>5</sub>CN and PdSe<sub>2</sub> monolayer. The sensitivity of PdSe<sub>2</sub> monolayer to C<sub>2</sub>F<sub>5</sub>CN was up to 68.61 %. Therefore, PdSe<sub>2</sub> monolayer has the potential of selective detection of C<sub>2</sub>F<sub>5</sub>CN gas sensing materials, and the findings in this paper provide theoretical guidance for the development of PdSe<sub>2</sub> monolayer gas sensing sensors for monitoring C<sub>4</sub>F<sub>7</sub>N insulation equipment.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114905"},"PeriodicalIF":3.0,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142422842","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}
Pub Date : 2024-10-01DOI: 10.1016/j.comptc.2024.114903
Hanwen Hu , Wujie Qiu , Jifen Wang
Ti3C2 MXene, a member of the two-dimensional (2D) transition metal carbides family, has garnered significant attention for its exceptional photothermal properties. To understand the mechanistic underpinnings of this feature, we conducted a comprehensive first-principles density functional theory analysis. This study was aimed at investigating the electronic band structure and vibrational characteristics of Ti3C2 MXene to unravel its microscopic process of photothermal conversion. After obtaining its optical and thermal properties, the process by which the material moves from light absorption to heat release is elucidated. The presence of localized surface plasmon resonance (LSPR) effects in Ti3C2 is proved by Finite-difference time-domain (FDTD) simulations. The synergy between the high thermal conductivity network in the Ti layers and the LSPR phenomenon is believed to be responsible for the superior photothermal conversion capabilities. This investigation enhances the understanding of the intrinsic properties of Ti3C2 MXene, confirming its status as an ultrahigh photothermal conversion material.
{"title":"Exploring the thermal and optical characteristics of Ti3C2 MXene for enhanced photothermal conversion","authors":"Hanwen Hu , Wujie Qiu , Jifen Wang","doi":"10.1016/j.comptc.2024.114903","DOIUrl":"10.1016/j.comptc.2024.114903","url":null,"abstract":"<div><div>Ti<sub>3</sub>C<sub>2</sub> MXene, a member of the two-dimensional (2D) transition metal carbides family, has garnered significant attention for its exceptional photothermal properties. To understand the mechanistic underpinnings of this feature, we conducted a comprehensive first-principles density functional theory analysis. This study was aimed at investigating the electronic band structure and vibrational characteristics of Ti<sub>3</sub>C<sub>2</sub> MXene to unravel its microscopic process of photothermal conversion. After obtaining its optical and thermal properties, the process by which the material moves from light absorption to heat release is elucidated. The presence of localized surface plasmon resonance (LSPR) effects in Ti<sub>3</sub>C<sub>2</sub> is proved by Finite-difference time-domain (FDTD) simulations. The synergy between the high thermal conductivity network in the Ti layers and the LSPR phenomenon is believed to be responsible for the superior photothermal conversion capabilities. This investigation enhances the understanding of the intrinsic properties of Ti<sub>3</sub>C<sub>2</sub> MXene, confirming its status as an ultrahigh photothermal conversion material.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114903"},"PeriodicalIF":3.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142422931","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}
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