Pub Date : 2024-11-09DOI: 10.1016/j.comptc.2024.114974
Farag M. A. Altalbawy , Uday Abdul-Reda Hussein , Shelesh krishna saraswat , Lalji Baldaniya , Rekha M.M. , Guntaj J. , Anirudh Gupta , Zahraa Sabah Ghnim , Ali Fawzi Al-Hussainy , Saeb jasim al-shuwaili , Fadhil Faez Sead
The interaction of temozolamide anticancer drugs with transition metal (TM) adsorbed WSe2 nanosheets was examined using the first principles approach. Main electronic and geometric parameters were systematically analyzed to comprehensively evaluate the drug nanocarrier characteristics of the modified WSe2 systems. Pt, Pd and Ag binding on the surface of WSe2 leads to the favorable structures for drug sensing process. Our results suggested a stronger interaction between temozolamide anticancer drugs and Pt-adsorbed WSe2 nanosheets, indicating the prospects for drug delivery systems based on modified WSe2. The oxygen atoms of temozolamide drug are found to be more interactive than other atoms when approaching the Pt-adsorbed WSe2 substrates. The moderate adsorption energy and recovery time reveal the potentials of Pt-adsorbed WSe2 for proper adsorbing of temozolamide drug. This research aims at giving theoretical insights into the prospective application of TM adsorbed WSe2 systems as effective nanocarriers for temozolamide drugs.
{"title":"−DFT study of the adsorption of temozolamide anticancer drugs on the TM-adsorbed WSe2 nanocarriers: Applications to drug delivery systems","authors":"Farag M. A. Altalbawy , Uday Abdul-Reda Hussein , Shelesh krishna saraswat , Lalji Baldaniya , Rekha M.M. , Guntaj J. , Anirudh Gupta , Zahraa Sabah Ghnim , Ali Fawzi Al-Hussainy , Saeb jasim al-shuwaili , Fadhil Faez Sead","doi":"10.1016/j.comptc.2024.114974","DOIUrl":"10.1016/j.comptc.2024.114974","url":null,"abstract":"<div><div>The interaction of temozolamide anticancer drugs with transition metal (TM) adsorbed WSe<sub>2</sub> nanosheets was examined using the first principles approach. Main electronic and geometric parameters were systematically analyzed to comprehensively evaluate the drug nanocarrier characteristics of the modified WSe<sub>2</sub> systems. Pt, Pd and Ag binding on the surface of WSe<sub>2</sub> leads to the favorable structures for drug sensing process. Our results suggested a stronger interaction between temozolamide anticancer drugs and Pt-adsorbed WSe<sub>2</sub> nanosheets, indicating the prospects for drug delivery systems based on modified WSe<sub>2</sub>. The oxygen atoms of temozolamide drug are found to be more interactive than other atoms when approaching the Pt-adsorbed WSe<sub>2</sub> substrates. The moderate adsorption energy and recovery time reveal the potentials of Pt-adsorbed WSe<sub>2</sub> for proper adsorbing of temozolamide drug. This research aims at giving theoretical insights into the prospective application of TM adsorbed WSe<sub>2</sub> systems as effective nanocarriers for temozolamide drugs.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1243 ","pages":"Article 114974"},"PeriodicalIF":3.0,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142698690","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 : 2024-11-09DOI: 10.1016/j.comptc.2024.114942
Hanna D. Hobbs, Lowen M. Hobbs, Robert W. Zoellner
Density functional theory calculations, at the ωB97X-D/6-311+G* level of theory, were performed on homoleptic fluoro-copper complexes [CuFn]x, n = 1 through 6 and x = 3+ through 5−, to determine the highest positive and lowest negative copper oxidation states that can be supported in these complexes. Only singlet and doublet spin states were investigated. All fluoro-copper stoichiometries stabilized copper(III) or greater. However, some stoichiometries stabilized oxidation states up to copper(VI), and the greatest positive copper oxidation state was copper(VIII) in the distorted octahedral [CuF6]2+ cation. Oxidation states as negative as copper(–IV) in the diatomic [CuF]5− anion and copper(–III) in the triatomic [CuF2]5− were also observed as optimized minima, although no negative oxidation states were calculated to exist for fluoro-copper complexes containing more than two fluorine atoms. No singlet or doublet fluoro-copper complexes with charges more positive than 3+, more negative than 5−, or of Cu(VII), could be optimized.
{"title":"The limits of copper oxidation states from density functional theory computations: Fluoro-copper complexes, [CuFn]x, where n = 1 through 6 and x = 3+ through 5−","authors":"Hanna D. Hobbs, Lowen M. Hobbs, Robert W. Zoellner","doi":"10.1016/j.comptc.2024.114942","DOIUrl":"10.1016/j.comptc.2024.114942","url":null,"abstract":"<div><div>Density functional theory calculations, at the ωB97X-D/6-311+G* level of theory, were performed on homoleptic fluoro-copper complexes [CuF<em><sub>n</sub></em>]<em><sup>x</sup></em>, <em>n</em> = 1 through 6 and <em>x</em> = 3+ through 5−, to determine the highest positive and lowest negative copper oxidation states that can be supported in these complexes. Only singlet and doublet spin states were investigated. All fluoro-copper stoichiometries stabilized copper(III) or greater. However, some stoichiometries stabilized oxidation states up to copper(VI), and the greatest positive copper oxidation state was copper(VIII) in the distorted octahedral [CuF<sub>6</sub>]<sup>2+</sup> cation. Oxidation states as negative as copper(–IV) in the diatomic [CuF]<sup>5−</sup> anion and copper(–III) in the triatomic [CuF<sub>2</sub>]<sup>5−</sup> were also observed as optimized minima, although no negative oxidation states were calculated to exist for fluoro-copper complexes containing more than two fluorine atoms. No singlet or doublet fluoro-copper complexes with charges more positive than 3+, more negative than 5−, or of Cu(VII), could be optimized.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114942"},"PeriodicalIF":3.0,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657038","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 find a suitable sensitivity sensor for sarin molecule (GB) as a nerve agent, we have compared and contrasted the adsorption behavior of it on the exterior surfaces of the (4,0), (5,0), (6,0), (7,0) and (8,0) BNNTs, at B3LYP/6-311+G*. The equilibrium distances (RGB-BNNT), Eads., FMOs, Eg, DOS, D.M. (μ) and reactivity index are estimated for the adsorption process of GB on these BNNTs. The RGB-BNNT, Eads. and the electronic properties of the BNNTs are depend on the BNNT diameter and orientation of the GB molecule outside BNNTs. The shorter RGB-BNNT of 1.61 Å and Eads. of −12.58 kcal/mol reveals that the 40O conformer is the most favorable configuration in which oxygen atom of PO in GB molecule is situated above a boron atom of (4,0) BNNT. The longer RGB-BNNT of 3.81 Å and Eads. of −2.31 kcal/mol exhibits that the 80F conformer is the least favorable configuration in which florin atom of PF in GB molecule is situated above a boron atom of (8,0) BNNT. However, adsorption process is exothermic. By increasing of the BNNT’s diameter and in going from (4،0) to (8،0) GB-BNNT complex either for the orientated PO or PF site; Eg and D.M. values are increased via the adsorption process. Henceforth, the designed 40O and 80F systems energetically are anticipated as the most and the least favorable complex, via the strong chemisorption and physisorption, respectively.
{"title":"Adsorption of sarin on zigzag boron-nitride nanotubes (BNNTs) via DFT","authors":"Farnaz Behmagham , Sattar Arshadi , Esmail Vessally , Tural Gulu Naghiyev , Rovnag Rzayev , Dharmesh Sur , Subbulakshmi Ganesan","doi":"10.1016/j.comptc.2024.114976","DOIUrl":"10.1016/j.comptc.2024.114976","url":null,"abstract":"<div><div>To find a suitable sensitivity sensor for sarin molecule (<strong>GB</strong>) as a nerve agent, we have compared and contrasted the adsorption behavior of it on the exterior surfaces of the (4,0), (5,0), (6,0), (7,0) and (8,0) BNNTs, at B3LYP/6-311+G*. The equilibrium distances (R<sub>GB-BNNT</sub>), <em>E</em><sub>ads.</sub>, FMOs, <em>E</em><sub>g</sub>, DOS, D.M. (μ) and reactivity index are estimated for the adsorption process of <strong>GB</strong> on these BNNTs. The R<sub>GB-BNNT</sub>, <em>E</em><sub>ads.</sub> and the electronic properties of the BNNTs are depend on the BNNT diameter and orientation of the <strong>GB</strong> molecule outside BNNTs. The shorter R<sub>GB-BNNT</sub> of 1.61 Å and <em>E</em><sub>ads.</sub> of −12.58 kcal/mol reveals that the <strong>40O</strong> conformer is the most favorable configuration in which oxygen atom of P<img>O in <strong>GB</strong> molecule is situated above a boron atom of (4,0) BNNT. The longer R<sub>GB-BNNT</sub> of 3.81 Å and <em>E</em><sub>ads.</sub> of −2.31 kcal/mol exhibits that the <strong>80F</strong> conformer is the least favorable configuration in which florin atom of P<img>F in <strong>GB</strong> molecule is situated above a boron atom of (8,0) BNNT. However, adsorption process is exothermic. By increasing of the BNNT’s diameter and in going from <strong>(4،0)</strong> to <strong>(8،0)</strong> GB-BNNT complex either for the orientated P<img>O or P<img>F site; <em>E</em><sub>g</sub> and D.M. values are increased <em>via</em> the adsorption process. Henceforth, the designed <strong>40O</strong> and <strong>80F</strong> systems energetically are anticipated as the most and the least favorable complex, <em>via</em> the strong chemisorption and physisorption, respectively.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1243 ","pages":"Article 114976"},"PeriodicalIF":3.0,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142745386","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}
Here, we studied the stability, electronic characteristics, and HER catalytic performance of transition metal single atom catalysts, both with and without the presence of chlorine ligand. The findings indicate that all catalysts, except for Au, Au-Cl, Ag, Ag-Cl, are thermodynamically stable. We found 3d transition metals are more stable than those in the 4d and 5d series. Ag-Cl, Sc, Ag, Fe-Cl, and Cr-Cl have the poorest electrochemical stability. We found a negative Pearson correlation between Fermi energy and formation energy for TM-Cl, which is opposite to the trend observed for bare TM catalysts. The higher HER activity of chlorine bonded system for the early 3d TM suggests that the downshifting of the d-band center facilitates the activity. We also observed a periodic trend in the d-band center for both TM and TM-Cl systems. Mn-Cl, Cr-Cl, Ti-Cl, Fe-Cl, V-Cl and Zn emerged as the superior catalysts in our study series.
在此，我们研究了过渡金属单原子催化剂的稳定性、电子特性和 HER 催化性能，包括氯配体存在和不存在的情况。研究结果表明，除 Au、Au-Cl、Ag、Ag-Cl 外，所有催化剂都具有热力学稳定性。我们发现 3d 过渡金属比 4d 和 5d 系列的金属更稳定。Ag-Cl、Sc、Ag、Fe-Cl 和 Cr-Cl 的电化学稳定性最差。我们发现 TM-Cl 的费米能与形成能之间存在负的皮尔逊相关性，这与裸 TM 催化剂的趋势相反。早期 3d TM 的氯键体系具有更高的 HER 活性，这表明 d 带中心的下移促进了活性的提高。我们还观察到 TM 和 TM-Cl 体系的 d 波段中心呈周期性变化趋势。在我们的研究系列中，Mn-Cl、Cr-Cl、Ti-Cl、Fe-Cl、V-Cl 和 Zn 成为最优秀的催化剂。
{"title":"Computational screening and investigation of ligand effect on TM single atom catalyst for hydrogen evolution reaction","authors":"N.J. Hemavathi , Chiranjib Majumder , Suman Kalyan Sahoo","doi":"10.1016/j.comptc.2024.114981","DOIUrl":"10.1016/j.comptc.2024.114981","url":null,"abstract":"<div><div>Here, we studied the stability, electronic characteristics, and HER catalytic performance of transition metal single atom catalysts, both with and without the presence of chlorine ligand. The findings indicate that all catalysts, except for Au, Au-Cl, Ag, Ag-Cl, are thermodynamically stable. We found 3d transition metals are more stable than those in the 4d and 5d series. Ag-Cl, Sc, Ag, Fe-Cl, and Cr-Cl have the poorest electrochemical stability. We found a negative Pearson correlation between Fermi energy and formation energy for TM-Cl, which is opposite to the trend observed for bare TM catalysts. The higher HER activity of chlorine bonded system for the early 3d TM suggests that the downshifting of the d-band center facilitates the activity. We also observed a periodic trend in the d-band center for both TM and TM-Cl systems. Mn-Cl, Cr-Cl, Ti-Cl, Fe-Cl, V-Cl and Zn emerged as the superior catalysts in our study series.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114981"},"PeriodicalIF":3.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657037","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 : 2024-11-08DOI: 10.1016/j.comptc.2024.114951
Yue-hong Yin, Chao Lu
Non-covalent interactions play an important role in numerous fields, particularly in physical hydrogen storage. The hydrogen storage properties of C3N are investigated by DFT calculations. The results indicated that H2 and C3N form physical adsorption. The electronic structure analysis demonstrates that both the covalent and electrostatic interactions between H2 and C3N are rather weak, while IRI analysis reveals that their interactions belong to non-valent interactions, and the further energy decomposition based on SAPT suggests that the sources of interaction energies differ for the two configurations TCR and TNR. For TCR, the induction energy is the primary contributor, for TNR, the electrostatic interaction dominates. Our comprehensive study not only enhances our understanding of the intricate interactions between H2 and C3N but also serves as a valuable guide for enhancing the adsorption strength in physical hydrogen storage systems.
{"title":"The non-covalent interaction between C3N and H2","authors":"Yue-hong Yin, Chao Lu","doi":"10.1016/j.comptc.2024.114951","DOIUrl":"10.1016/j.comptc.2024.114951","url":null,"abstract":"<div><div>Non-covalent interactions play an important role in numerous fields, particularly in physical hydrogen storage. The hydrogen storage properties of C<sub>3</sub>N are investigated by DFT calculations. The results indicated that H<sub>2</sub> and C<sub>3</sub>N form physical adsorption. The electronic structure analysis demonstrates that both the covalent and electrostatic interactions between H<sub>2</sub> and C<sub>3</sub>N are rather weak, while IRI analysis reveals that their interactions belong to non-valent interactions, and the further energy decomposition based on SAPT suggests that the sources of interaction energies differ for the two configurations T<sub><span>CR</span></sub> and T<sub><span>NR</span></sub>. For T<sub><span>CR</span></sub>, the induction energy is the primary contributor, for T<sub><span>NR</span></sub>, the electrostatic interaction dominates. Our comprehensive study not only enhances our understanding of the intricate interactions between H<sub>2</sub> and C<sub>3</sub>N but also serves as a valuable guide for enhancing the adsorption strength in physical hydrogen storage systems.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114951"},"PeriodicalIF":3.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657674","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}
Singlet fission (SF) suffers from the scarcity of available SF chromophores and sensitizers. Tetracene, pentacene and their derivatives, are two typical model systems for the study of SF photophysical phenomena. Herein, the analogues of polyacenes, furanoacenes and their derivatives, were evaluated as potential SF chromophores and sensitizers through a theoretical study. The primary photostability were evaluated by the frontier molecular orbital energy levels, diradical characters and SF relevant excited state energies according to the type-I and −II photodegradation mechanisms. The cross-substitutions by combining central substitutions with triple bonds and terminal substituents enhance photostability, tune the SF relevant excited states efficiently, and give more appropriate E(T1) to be SF sensitizers. This work helps to give better understanding of the electronic structures and SF capability of furanoacenes.
单裂变（SF）的问题在于可用的 SF 发色团和敏化剂稀缺。四碳烯、五碳烯及其衍生物是研究 SF 光物理现象的两个典型模型系统。在此，我们通过理论研究评估了作为潜在 SF 发色团和敏化剂的聚碳酸酯类似物、呋喃烯及其衍生物。根据 I 型和 II 型光降解机制，通过前沿分子轨道能级、二极性特征和 SF 相关激发态能量评估了主要光稳定性。通过将中心取代与三键和末端取代基相结合的交叉取代，提高了光稳定性，有效地调节了与 SF 有关的激发态，并给出了更合适的 E（T1），从而成为 SF 增敏剂。这项工作有助于更好地理解呋喃并烯类化合物的电子结构和 SF 能力。
{"title":"Molecular design of furanoacene-based singlet fission sensitizers combining diradical character and cross-substitution","authors":"Li shen, Zhanqing Chang, Changhao Zhang, Mengyao Zhu, Xiaobo Gao, Xinwei Liu, Yue Li, Jitao Lu, Qian Wu, Qingguo Meng","doi":"10.1016/j.comptc.2024.114982","DOIUrl":"10.1016/j.comptc.2024.114982","url":null,"abstract":"<div><div>Singlet fission (SF) suffers from the scarcity of available SF chromophores and sensitizers. Tetracene, pentacene and their derivatives, are two typical model systems for the study of SF photophysical phenomena. Herein, the analogues of polyacenes, furanoacenes and their derivatives, were evaluated as potential SF chromophores and sensitizers through a theoretical study. The primary photostability were evaluated by the frontier molecular orbital energy levels, diradical characters and SF relevant excited state energies according to the type-I and −II photodegradation mechanisms. The cross-substitutions by combining central substitutions with triple bonds and terminal substituents enhance photostability, tune the SF relevant excited states efficiently, and give more appropriate <em>E</em>(T<sub>1</sub>) to be SF sensitizers. This work helps to give better understanding of the electronic structures and SF capability of furanoacenes.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114982"},"PeriodicalIF":3.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657519","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 : 2024-11-07DOI: 10.1016/j.comptc.2024.114936
Fazal Dayan, Adnan Shahzad, Imad Ud Din
Identifying new electrode materials for K-ion batteries (KIBs) is still difficult since battery technology lacks an effective high-throughput screening approach. The durability, affordability, safety, and resemblance to Li-ion batteries of KIBs have garnered them tremendous attention. Porphyrin-based materials have become attractive options because of their generous surface area and advantageous photo-physical characteristics. As effective cathodic materials for KIBs, porphyrin Schiff base nanostructures (SBNs) are suggested in this work. Our goal was to improve Potassium-ion doped porphyrin derivatives by using Density Functional Theory (DFT) with the Gaussian 09 program with a B3LYP/6-31G(d) basis set. We also calculated important electronic parameters such as the band gap, electrophilicity, chemical potential, and frontier orbitals (HOMO and LUMO). The determined HOMO-LUMO gaps for compounds 1 to 4 were 2.97, 1.52, 1.38, and 1.36 respectively. The computed gaps indicate that the reactivity of the compounds increases from 1 to 4, whereas the stability decreases from 1 to 4.
Based on these computational observations, it is expected that this theoretical analysis will provide a basis for future researchers to explore the practical applications of these compounds through experimentation.
{"title":"Designing and investigating electronic states of porphyrin Schiff bases nanoflakes, cathode materials for K+ - batteries","authors":"Fazal Dayan, Adnan Shahzad, Imad Ud Din","doi":"10.1016/j.comptc.2024.114936","DOIUrl":"10.1016/j.comptc.2024.114936","url":null,"abstract":"<div><div>Identifying new electrode materials for K-ion batteries (KIBs) is still difficult since battery technology lacks an effective high-throughput screening approach. The durability, affordability, safety, and resemblance to Li-ion batteries of KIBs have garnered them tremendous attention. Porphyrin-based materials have become attractive options because of their generous surface area and advantageous photo-physical characteristics. As effective cathodic materials for KIBs, porphyrin Schiff base nanostructures (SBNs) are suggested in this work. Our goal was to improve Potassium-ion doped porphyrin derivatives by using Density Functional Theory (DFT) with the Gaussian 09 program with a B3LYP/6-31G(d) basis set. We also calculated important electronic parameters such as the band gap, electrophilicity, chemical potential, and frontier orbitals (HOMO and LUMO). The determined HOMO-LUMO gaps for compounds <strong>1</strong> to <strong>4</strong> were 2.97, 1.52, 1.38, and 1.36 respectively. The computed gaps indicate that the reactivity of the compounds increases from <strong>1</strong> to <strong>4</strong>, whereas the stability decreases from <strong>1</strong> to <strong>4</strong>.</div><div>Based on these computational observations, it is expected that this theoretical analysis will provide a basis for future researchers to explore the practical applications of these compounds through experimentation.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114936"},"PeriodicalIF":3.0,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657675","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}
We investigated the effects of externally applied pressure on the Sr2P7Br compound’s properties, specifically its crystalline structure, elasticity, and thermodynamics. This investigation was carried out using the pseudopotential plane wave method within the framework of density functional theory. We used the well-known PBEsol variant of the exchange–correlation general gradient approximation specifically designed for solid-state analysis. This is the first endeavor to investigate the effects of pressure on the Sr2P7Br material using a theoretical approach. The computed equilibrium structural parameters closely match the relevant experimental counterpart values. The determined elastic constants, obtained under both ambient pressure and hydrostatic pressures up to 18 GPa, satisfy the mechanical stability requirements. Based on the computed Pugh’s ratio, Cauchy pressure, and Poisson’s ratio, it can be concluded that the Sr2P7Br compound exhibits ductile behavior. The polycrystalline elastic moduli, including the isotropic bulk modulus, shear modulus, Young’s modulus, and Poisson’s ratio, at ambient pressure and under pressure effects, were derived from the single-crystal elastic constants. Additionally, associated parameters, such as average sound velocity, Debye temperature, minimum thermal conductivity, and Vickers hardness, were examined under pressure influences. The quasi-harmonic Debye approximation was used to investigate the relationship between temperature and some macroscopic physical parameters, such as lattice parameter, bulk modulus, Debye temperature, volume thermal expansion coefficient, and isobaric and isochoric heat capacities, at fixed pressures of 0, 4, 8, 12, and 16 GPa. The results derived from the elastic constants exhibit substantial concordance with those computed using the Debye quasi-harmonic model, thereby validating the reliability of our findings.
{"title":"The Structural, Elastic, and thermodynamic properties of Sr2P7Br Double Zintl salt with heptaphosphanortricyclane configuration","authors":"Missoum Radjai , Saber Saad Essaoud , Abdelmadjid Bouhemadou , Djamel Allali , Abdelhak Bedjaoui","doi":"10.1016/j.comptc.2024.114947","DOIUrl":"10.1016/j.comptc.2024.114947","url":null,"abstract":"<div><div>We investigated the effects of externally applied pressure on the Sr<sub>2</sub>P<sub>7</sub>Br compound’s properties, specifically its crystalline structure, elasticity, and thermodynamics. This investigation was carried out using the pseudopotential plane wave method within the framework of density functional theory. We used the well-known PBEsol variant of the exchange–correlation general gradient approximation specifically designed for solid-state analysis. This is the first endeavor to investigate the effects of pressure on the Sr<sub>2</sub>P<sub>7</sub>Br material using a theoretical approach. The computed equilibrium structural parameters closely match the relevant experimental counterpart values. The determined elastic constants, obtained under both ambient pressure and hydrostatic pressures up to 18 GPa, satisfy the mechanical stability requirements. Based on the computed Pugh’s ratio, Cauchy pressure, and Poisson’s ratio, it can be concluded that the Sr<sub>2</sub>P<sub>7</sub>Br compound exhibits ductile behavior. The polycrystalline elastic moduli, including the isotropic bulk modulus, shear modulus, Young’s modulus, and Poisson’s ratio, at ambient pressure and under pressure effects, were derived from the single-crystal elastic constants. Additionally, associated parameters, such as average sound velocity, Debye temperature, minimum thermal conductivity, and Vickers hardness, were examined under pressure influences. The quasi-harmonic Debye approximation was used to investigate the relationship between temperature and some macroscopic physical parameters, such as lattice parameter, bulk modulus, Debye temperature, volume thermal expansion coefficient, and isobaric and isochoric heat capacities, at fixed pressures of 0, 4, 8, 12, and 16 GPa. The results derived from the elastic constants exhibit substantial concordance with those computed using the Debye quasi-harmonic model, thereby validating the reliability of our findings.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114947"},"PeriodicalIF":3.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657638","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 : 2024-11-06DOI: 10.1016/j.comptc.2024.114977
Subhadip Ghosh, Prasanta K. Nandi
Nanographenes (NGs) are a distinct section of graphene in which the dangling bonds are saturated with hydrogen atoms (C42H18). This confinement in size results in unique properties and potential applications. The density functional theory (DFT) is used to investigate the reactivity and electronic sensitivity of a model carborazine (B2C2N2) ring doped nanographene (CBNG) for detecting NO2 gas. In CBNG/NO2 complex, one oxygen atom of the NO2 molecule is positioned at a distance of 2.93Ả from the center of the B2C2N2 ring, with an adsorption energy −6.2 kcal/mol. The adsorption energy of NO2 on CBNG is apparently larger than those of other gas molecules, which fall between the suitable range of strong physical adsorption and weak chemical adsorption. Upon NO2 adsorption, the band gap of CBNG sheet reaches 62.4 %. The outcome of the present study may be exploited in the industry, particularly in the synthesis of effective NO2 gas sensors.
{"title":"Carborazine doped nanographene (CBNG) sheet as a promising NO2 gas sensor: A theoretician’s approach","authors":"Subhadip Ghosh, Prasanta K. Nandi","doi":"10.1016/j.comptc.2024.114977","DOIUrl":"10.1016/j.comptc.2024.114977","url":null,"abstract":"<div><div>Nanographenes (NGs) are a distinct section of graphene in which the dangling bonds are saturated with hydrogen atoms (C<sub>42</sub>H<sub>18</sub>). This confinement in size results in unique properties and potential applications. The density functional theory (DFT) is used to investigate the reactivity and electronic sensitivity of a model carborazine (B<sub>2</sub>C<sub>2</sub>N<sub>2</sub>) ring doped nanographene (CBNG) for detecting NO<sub>2</sub> gas. In CBNG/NO<sub>2</sub> complex, one oxygen atom of the NO<sub>2</sub> molecule is positioned at a distance of 2.93Ả from the center of the B<sub>2</sub>C<sub>2</sub>N<sub>2</sub> ring, with an adsorption energy −6.2 kcal/mol. The adsorption energy of NO<sub>2</sub> on CBNG is apparently larger than those of other gas molecules, which fall between the suitable range of strong physical adsorption and weak chemical adsorption. Upon NO<sub>2</sub> adsorption, the band gap of CBNG sheet reaches 62.4 %. The outcome of the present study may be exploited in the industry, particularly in the synthesis of effective NO<sub>2</sub> gas sensors.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114977"},"PeriodicalIF":3.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657633","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 : 2024-11-06DOI: 10.1016/j.comptc.2024.114955
Sneha Upadhyay , Pankaj Srivastava
Phosphorene, due to its remarkable semiconducting properties, prevailed as principal material of research for decades. The substitutional doping of carbon (C), silicon (Si), oxygen (O) and sulphur (S) atom was reported earlier. DFT studies are done towards the unexplored area of sodium (Na) adsorption and diffusion over these doped phosphorene structures. The effective adsorption energies for C-, Si-, O- and S- doped phosphorene are −3.19 eV, −2.63 eV, −3.12 eV and −2.39 eV respectively. The minimum value of activation energies are 0.68 eV, 0.45 eV, 1.00 eV and 0.26 eV respectively. Hence the diffusion and intercalation–deintercalation process seem to be supportive. The lattice integrity is maintained in the whole process. Good amount of charge transfer shows better conductivity supported by band structure and density of states diagrams. Based on these data, the proposed doped phosphorene configurations can be predicted suitable for further studies towards anode application in Na-ion battery.
{"title":"First-principles study of sodium adsorption and diffusion over substitutionally doped phosphorene","authors":"Sneha Upadhyay , Pankaj Srivastava","doi":"10.1016/j.comptc.2024.114955","DOIUrl":"10.1016/j.comptc.2024.114955","url":null,"abstract":"<div><div>Phosphorene, due to its remarkable semiconducting properties, prevailed as principal material of research for decades. The substitutional doping of carbon (C), silicon (Si), oxygen (O) and sulphur (S) atom was reported earlier. DFT studies are done towards the unexplored area of sodium (Na) adsorption and diffusion over these doped phosphorene structures. The effective adsorption energies for C-, Si-, O- and S- doped phosphorene are −3.19 eV, −2.63 eV, −3.12 eV and −2.39 eV respectively. The minimum value of activation energies are 0.68 eV, 0.45 eV, 1.00 eV and 0.26 eV respectively. Hence the diffusion and intercalation–deintercalation process seem to be supportive. The lattice integrity is maintained in the whole process. Good amount of charge transfer shows better conductivity supported by band structure and density of states diagrams. Based on these data, the proposed doped phosphorene configurations can be predicted suitable for further studies towards anode application in Na-ion battery.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114955"},"PeriodicalIF":3.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657635","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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