Pub Date : 2024-11-03DOI: 10.1016/j.comptc.2024.114971
O. Baraka , M. Fodil , A. Mokadem , Mohammed Benali Kanoun , Souraya Goumri-Said
The Mn+1AXn phases, known for their unique combination of metallic and ceramic properties, have attracted significant attention due to their potential applications in extreme environments. In this study, we use density functional theory to investigate the structural, electronic, elastic, mechanical, and thermodynamic properties of V2SnX (X = B and N) compounds. Our results confirm that both compounds are elastically, thermodynamically, and dynamically stable, with a ductile nature. The metallic behavior is further supported by electronic band structures and density of states analysis, with V-d states playing a key role in electrical conductivity. Using the quasi-harmonic Debye model, we also examine the effects of temperature and pressure, finding that the bulk modulus and Debye temperature decrease with rising pressure below 50 GPa. Based on these findings, V2SnX compounds are ideal candidates for high-performance applications in harsh conditions, where materials need to maintain stability, conductivity, and resistance to thermal and mechanical stress.
{"title":"A Comparative analysis of the physical properties of predicted MAX phases V2SnN and V2SnB with the synthesized V2SnC: Insights from DFT calculations","authors":"O. Baraka , M. Fodil , A. Mokadem , Mohammed Benali Kanoun , Souraya Goumri-Said","doi":"10.1016/j.comptc.2024.114971","DOIUrl":"10.1016/j.comptc.2024.114971","url":null,"abstract":"<div><div>The M<sub>n+1</sub>AX<sub>n</sub> phases, known for their unique combination of metallic and ceramic properties, have attracted significant attention due to their potential applications in extreme environments. In this study, we use density functional theory to investigate the structural, electronic, elastic, mechanical, and thermodynamic properties of V<sub>2</sub>SnX (X = B and N) compounds. Our results confirm that both compounds are elastically, thermodynamically, and dynamically stable, with a ductile nature. The metallic behavior is further supported by electronic band structures and density of states analysis, with V-<em>d</em> states playing a key role in electrical conductivity. Using the quasi-harmonic Debye model, we also examine the effects of temperature and pressure, finding that the bulk modulus and Debye temperature decrease with rising pressure below 50 GPa. Based on these findings, V<sub>2</sub>SnX compounds are ideal candidates for high-performance applications in harsh conditions, where materials need to maintain stability, conductivity, and resistance to thermal and mechanical stress.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114971"},"PeriodicalIF":3.0,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657632","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 : 2024-11-02DOI: 10.1016/j.comptc.2024.114949
Bayan Azizi , Rovnag Rzayev , Esmail Vessally
Based on density functional theory calculations, NO2 and SO2 adsorptions on the Ag- and Au-functionalized silicene nanosheets were theoretically examined to explore the potential of the modified silicene nanosheets as efficient gas sensors. According to band structure analysis, both Ag- and Au-functionalized silicene nanosheets revealed metallic behavior. The results on the NO2 and SO2 adsorptions on Ag- and Au-functionalized silicene monolayer indicate that both substrates can strongly adsorb the gas molecules with large adsorption energies. There are large charge accumulation between the Au/Ag and Si atoms, which represents the significant connection between these atoms. The large overlaps of the PDOS spectra of the Au and O atoms represent the covalent nature of bonding between them. These insights suggest that Ag and Au can be appropriate adatoms functionalized on the silicene nanosheets for detecting NO2 and SO2 molecules.
基于密度泛函理论计算，从理论上研究了氮氧化物和二氧化硫在琼脂和金功能化硅纳米片上的吸附情况，以探索改性硅纳米片作为高效气体传感器的潜力。根据能带结构分析，Ag 和 Au 功能化硅纳米片都显示出金属特性。二氧化氮和二氧化硫在 Ag- 和 Au-功能化硅单层上的吸附结果表明，这两种基底都能以较大的吸附能强烈吸附气体分子。金/银原子和硅原子之间存在大量电荷积累，这表明这些原子之间存在重要联系。Au 原子和 O 原子的 PDOS 光谱的大量重叠代表了它们之间的共价键性质。这些发现表明，硅纳米片上的 Ag 和 Au 原子是检测二氧化氮和二氧化硫分子的合适功能原子。
{"title":"Enhanced chemical activity and gas sensing performance of silicene nanosheets by noble metal (Au, Ag) decoration: A DFT study","authors":"Bayan Azizi , Rovnag Rzayev , Esmail Vessally","doi":"10.1016/j.comptc.2024.114949","DOIUrl":"10.1016/j.comptc.2024.114949","url":null,"abstract":"<div><div>Based on density functional theory calculations, NO<sub>2</sub> and SO<sub>2</sub> adsorptions on the Ag- and Au-functionalized silicene nanosheets were theoretically examined to explore the potential of the modified silicene nanosheets as efficient gas sensors. According to band structure analysis, both Ag- and Au-functionalized silicene nanosheets revealed metallic behavior. The results on the NO<sub>2</sub> and SO<sub>2</sub> adsorptions on Ag- and Au-functionalized silicene monolayer indicate that both substrates can strongly adsorb the gas molecules with large adsorption energies. There are large charge accumulation between the Au/Ag and Si atoms, which represents the significant connection between these atoms. The large overlaps of the PDOS spectra of the Au and O atoms represent the covalent nature of bonding between them. These insights suggest that Ag and Au can be appropriate adatoms functionalized on the silicene nanosheets for detecting NO<sub>2</sub> and SO<sub>2</sub> molecules.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114949"},"PeriodicalIF":3.0,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142587479","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 : 2024-11-02DOI: 10.1016/j.comptc.2024.114972
Bassey O. Ekpong , Miracle N. Ogbogu , Henry O. Edet , Emmanuel Emmanuel
The development of new approaches or approaches for the detection of methylmalonic acid from biological samples is now necessary for early diagnosis of vitamin B12 deficiency and appropriate treatment. In this study, Yttrium-encapsulated fullerene (Y@C80) doped with arsenic (As), bismuth (Bi), phosphorous (P), and antimony (Sb) was investigated for its ability to sense methylmalonic acid (MMA) as a biomarker using M06-2X/GenECP/def2svp/LanL2DZ method. The nanostructural analysis showed a marginal deviation in the bond lengths between atoms of the structure upon optimization of the structures interacting with the MMA biomarker, which demonstrated the stability of the system for sensing. The HOMO-LUMO reactivity descriptor revealed that the compound was reactive toward the sensing of the MMA biomarker, as the various systems MMA_As_Y@C80, MMA_Bi_Y@C80, MMA_P_Y@C80, and MMA_Sb_Y@C80 demonstrated relatively short energy gaps of 2.039 eV, 2.025 eV, 2.135 eV, and 2.023 eV, respectively. The nanomaterial strongly adsorbed the biomarker, as indicated by the negative adsorption energies of −0.47075 eV, −0.70478 eV, 0.9034 eV, and −0.5388 eV corresponding to MMA_As_Y@C80, MMA_Bi_Y@C80, MMA_P_Y@C80, and MMA_Sb_Y@C80, respectively; however, MMA-P-Y@C80 showed a weaker ability to sense the biomarker. Additionally, the recovery time after the detection of the biomarker was relatively short, comparable to the increase in the adsorption strength, with MMA-Bi-Y@C80 having the shortest recovery time (3.829 × 10−37). This is significant for the development of a highly sensitive and efficient technique for methylmalonic acid (MMA) biomarker sensing.
{"title":"Yttrium-encapsulated fullerene (Y@C80) mono-doping with As, Bi, Sb, and P for the enhanced sensing of methylmalonic acid (MMA) as a biomarker for vitamin B12 deficiency: A DFT study","authors":"Bassey O. Ekpong , Miracle N. Ogbogu , Henry O. Edet , Emmanuel Emmanuel","doi":"10.1016/j.comptc.2024.114972","DOIUrl":"10.1016/j.comptc.2024.114972","url":null,"abstract":"<div><div>The development of new approaches or approaches for the detection of methylmalonic acid from biological samples is now necessary for early diagnosis of vitamin B<sub>12</sub> deficiency and appropriate treatment. In this study, Yttrium-encapsulated fullerene (Y@C<sub>80</sub>) doped with arsenic (As), bismuth (Bi), phosphorous (P), and antimony (Sb) was investigated for its ability to sense methylmalonic acid (MMA) as a biomarker using M06-2X/GenECP/def2svp/LanL2DZ method. The nanostructural analysis showed a marginal deviation in the bond lengths between atoms of the structure upon optimization of the structures interacting with the MMA biomarker, which demonstrated the stability of the system for sensing. The HOMO-LUMO reactivity descriptor revealed that the compound was reactive toward the sensing of the MMA biomarker, as the various systems MMA_As_Y@C<sub>80</sub>, MMA_Bi_Y@C<sub>80</sub>, MMA_P_Y@C<sub>80</sub>, and MMA_Sb_Y@C<sub>80</sub> demonstrated relatively short energy gaps of 2.039 eV, 2.025 eV, 2.135 eV, and 2.023 eV, respectively. The nanomaterial strongly adsorbed the biomarker, as indicated by the negative adsorption energies of −0.47075 eV, −0.70478 eV, 0.9034 eV, and −0.5388 eV corresponding to MMA_As_Y@C<sub>80</sub>, MMA_Bi_Y@C<sub>80</sub>, MMA_P_Y@C<sub>80</sub>, and MMA_Sb_Y@C<sub>80</sub>, respectively; however, MMA-P-Y@C<sub>80</sub> showed a weaker ability to sense the biomarker. Additionally, the recovery time after the detection of the biomarker was relatively short, comparable to the increase in the adsorption strength, with MMA-Bi-Y@C<sub>80</sub> having the shortest recovery time (3.829 × 10<sup>−37</sup>). This is significant for the development of a highly sensitive and efficient technique for methylmalonic acid (MMA) biomarker sensing.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114972"},"PeriodicalIF":3.0,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657673","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 : 2024-11-01DOI: 10.1016/j.comptc.2024.114948
Pedro Oliveira Mariz de Carvalho, Rogério Custodio
An alternative approach is introduced for accurately describe atomic orbitals using an integral transform of Gaussian-type basis functions (GTO) combined with continuous and analytical weight functions. The functional form of these weight functions was optimized using the variational criterion, achieving μHartree-level precision in energy calculations for atoms, monovalent ions up to the third period of the periodic table, and the H2 molecule. However, errors increased for heavier atoms, such as sulfur and chlorine, indicating the need for further refinement of the weight functions. This approach enhances the accuracy of electronic structure calculations, offering a rigorous alternative for deriving one-electron wave functions from discrete basis sets and vice-versa for atoms and molecules.
{"title":"Continuous approximation for linear combination coefficients: Exploring a neglected concept","authors":"Pedro Oliveira Mariz de Carvalho, Rogério Custodio","doi":"10.1016/j.comptc.2024.114948","DOIUrl":"10.1016/j.comptc.2024.114948","url":null,"abstract":"<div><div>An alternative approach is introduced for accurately describe atomic orbitals using an integral transform of Gaussian-type basis functions (GTO) combined with continuous and analytical weight functions. The functional form of these weight functions was optimized using the variational criterion, achieving μHartree-level precision in energy calculations for atoms, monovalent ions up to the third period of the periodic table, and the H<sub>2</sub> molecule. However, errors increased for heavier atoms, such as sulfur and chlorine, indicating the need for further refinement of the weight functions. This approach enhances the accuracy of electronic structure calculations, offering a rigorous alternative for deriving one-electron wave functions from discrete basis sets and vice-versa for atoms and molecules.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114948"},"PeriodicalIF":3.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142587482","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 : 2024-11-01DOI: 10.1016/j.comptc.2024.114956
Michele De Rosa, Simone Morpurgo
Two extended clusters representing different portions of Cu-ZSM-5 were treated within a two-layer ONIOM approximation, employing DFT calculations for both the real and the model system. Despite a two-step optimization procedure successfully employed in previous work, a consistent number of imaginary and anomalous frequencies appeared after the vibrational analysis. These artefacts depend both on the basis set assigned to link atoms and on an improper setting of the O–H distances, where H are the link atoms at the boundaries of the model system. The latter problem, revealed for the first time in the present study, originates from the default scale factor employed by the ONIOM routine within Gaussian-09. Once basis set and g scale factor are properly set, all imaginary and anomalous frequencies disappear. The present findings may represent an interesting and practical solution to an annoying computational problem, whenever it occurs in the framework of ONIOM calculations.
代表 Cu-ZSM-5 不同部分的两个扩展簇在双层 ONIOM 近似方法中进行了处理，并对真实系统和模型系统进行了 DFT 计算。尽管在之前的工作中成功采用了两步优化程序，但振动分析后仍出现了大量虚频和异常频率。这些假象既取决于分配给链接原子的基集，也取决于 O-H 间距的不当设置，其中 H 是模型体系边界上的链接原子。后一个问题是本研究首次发现的，它源于高斯-09 中 ONIOM 例程使用的默认比例因子。一旦正确设置了基集和 g 比例因子，所有虚频和异常频率都会消失。只要在 ONIOM 计算框架中出现恼人的计算问题，本研究结果可能是一个有趣而实用的解决方案。
{"title":"How to get rid of imaginary frequencies within ONIOM geometry optimizations: A DFT study on the effect of basis set and link atom distances in Cu-ZSM-5","authors":"Michele De Rosa, Simone Morpurgo","doi":"10.1016/j.comptc.2024.114956","DOIUrl":"10.1016/j.comptc.2024.114956","url":null,"abstract":"<div><div>Two extended clusters representing different portions of Cu-ZSM-5 were treated within a two-layer ONIOM approximation, employing DFT calculations for both the real and the model system. Despite a two-step optimization procedure successfully employed in previous work, a consistent number of imaginary and anomalous frequencies appeared after the vibrational analysis. These artefacts depend both on the basis set assigned to link atoms and on an improper setting of the O–H distances, where H are the link atoms at the boundaries of the model system. The latter problem, revealed for the first time in the present study, originates from the default scale factor employed by the ONIOM routine within Gaussian-09. Once basis set and <em>g</em> scale factor are properly set, all imaginary and anomalous frequencies disappear. The present findings may represent an interesting and practical solution to an annoying computational problem, whenever it occurs in the framework of ONIOM calculations.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114956"},"PeriodicalIF":3.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657668","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}
Sertraline is a selective serotonin reuptake inhibitor (SSRI) widely used as an antidepressant. The presence of HCl in forming sertraline hydrochloride affects its physicochemical properties. This article aimed to understand the molecular and electronic structures of sertraline hydrochloride. For this, theoretical calculations were carried out at the DFT/M06-2X/6-311++G(d,p) level of theory. The molecular topology was studied. In the case of the C10–H⋯Cl interaction, the Hirshfeld surface showed that the contacts between the H atom and the Cl anion equal the sum of the van der Waals radii. This structure is susceptible to electrophilic attacks according to the Fukui function. Frontier molecular orbital (HOMO and LUMO) showed that the presence of HCl increased the acidic character of the sertraline. Topological analysis of SERTH showed that NH⋯Cl hydrogen bond type interactions are predominant and contribute to the stability of the crystal.
{"title":"A comprehensive molecular description of sertraline hydrochloride: From solid state to electronic structure","authors":"A.C.B. Morais , A.S.N. Aguiar , P. Perjesi , H.B. Napolitano , L.L. Borges","doi":"10.1016/j.comptc.2024.114957","DOIUrl":"10.1016/j.comptc.2024.114957","url":null,"abstract":"<div><div>Sertraline is a selective serotonin reuptake inhibitor (SSRI) widely used as an antidepressant. The presence of HCl in forming sertraline hydrochloride affects its physicochemical properties. This article aimed to understand the molecular and electronic structures of sertraline hydrochloride. For this, theoretical calculations were carried out at the DFT/M06-2X/6-311++G(d,p) level of theory. The molecular topology was studied. In the case of the C10–H⋯Cl interaction, the Hirshfeld surface showed that the contacts between the H atom and the Cl anion equal the sum of the van der Waals radii. This structure is susceptible to electrophilic attacks according to the Fukui function. Frontier molecular orbital (HOMO and LUMO) showed that the presence of HCl increased the acidic character of the sertraline. Topological analysis of SERTH showed that N<img>H⋯Cl hydrogen bond type interactions are predominant and contribute to the stability of the crystal.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114957"},"PeriodicalIF":3.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593357","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 : 2024-10-30DOI: 10.1016/j.comptc.2024.114950
Jing Yi , Tong Yan , Anqi Li , Changluo Zheng , Lidong Zhang , Longwei Cheng , Lili Lei , Pan Wang
Small-molecule nitrogen-containing contaminants can be produced by the pyrolysis of diethylamine (DEA) alone or in conjunction with other molecules. To investigate the theoretical chemistry of the combustion of DEA, the CBS method determines the potential energy surface and the rate constants are calculated based on a combination of RRKM and TST theories. The H-abstraction reactions by H radicals are more kinetically advantageous. Site α has the most difficult H-abstraction procedure, but site γ has the competitive capacity to form subsequent products. The H-abstraction by NO2 radical produces trans-HONO, cis-HONO, and HNO2. For the reaction channels of DEA radicals, decomposition reactions have more kinetic advantages than isomerization. Kinetic parameters were obtained and the model was modified based on the fitted rate constants. The modified model has better predictive ability at low temperatures. This work provides extensive data to improve the modeling of DEA combustion at low and medium temperatures.
二乙胺（DEA）单独或与其他分子一起热解可产生小分子含氮污染物。为了研究二乙胺燃烧的理论化学性质，CBS 方法确定了势能面，并根据 RRKM 和 TST 理论组合计算了速率常数。通过 H 自由基进行的 H 萃取反应在动力学上更具优势。位点 α 的吸氢过程最为困难，但位点 γ 具有形成后续产物的竞争能力。NO2 自由基萃取 H 会产生反式-HONO、顺式-HONO 和 HNO2。在 DEA 自由基的反应通道中，分解反应比异构化反应具有更大的动力学优势。根据拟合的速率常数获得了动力学参数并修改了模型。修改后的模型在低温下具有更好的预测能力。这项工作为改进中低温下的 DEA 燃烧模型提供了大量数据。
{"title":"Theoretical and modeling studies on the kinetics of diethylamine dehydrogenation and subsequent isomerization and decomposition reactions","authors":"Jing Yi , Tong Yan , Anqi Li , Changluo Zheng , Lidong Zhang , Longwei Cheng , Lili Lei , Pan Wang","doi":"10.1016/j.comptc.2024.114950","DOIUrl":"10.1016/j.comptc.2024.114950","url":null,"abstract":"<div><div>Small-molecule nitrogen-containing contaminants can be produced by the pyrolysis of diethylamine (DEA) alone or in conjunction with other molecules. To investigate the theoretical chemistry of the combustion of DEA, the CBS method determines the potential energy surface and the rate constants are calculated based on a combination of RRKM and TST theories. The H-abstraction reactions by H radicals are more kinetically advantageous. Site α has the most difficult H-abstraction procedure, but site γ has the competitive capacity to form subsequent products. The H-abstraction by NO<sub>2</sub> radical produces <em>trans</em>-HONO, <em>cis</em>-HONO, and HNO<sub>2</sub>. For the reaction channels of DEA radicals, decomposition reactions have more kinetic advantages than isomerization. Kinetic parameters were obtained and the model was modified based on the fitted rate constants. The modified model has better predictive ability at low temperatures. This work provides extensive data to improve the modeling of DEA combustion at low and medium temperatures.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114950"},"PeriodicalIF":3.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657631","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 : 2024-10-30DOI: 10.1016/j.comptc.2024.114952
Wanjiang You , Hao Zou , Xiaoqiang Wang , Lielin Wang , Ning Pan , Fang Xiang
The present work investigated the adsorption of gaseous iodine molecules (I2) on stable CuS surface, which has demonstrated excellent performance as an adsorbent for I2 removal, with first-principles density functional theory (DFT). In this work, a pair of asymmetric surfaces (marked as slab1 and slab2) formed by breaking the weakest bond along (0 0 1) direction are chosen to present CuS surfaces. The findings indicate that the adsorption of I2 molecules on the pristine CuS(0 0 1) surface is relatively weak, while surface defects significantly enhance the binding strength of I2. In particular, S-vacancy CuS(0 0 1) surfaces exhibit considerably higher adsorption energy for I2 compared to Cu-vacancy surfaces. We found that the hollow and Cu-top sites are typically the dominant adsorption sites, and the initial orientation of I2 relative to the surface also influences the adsorption performance.
{"title":"First-principles density functional study of iodine molecule adsorption on stable CuS surfaces","authors":"Wanjiang You , Hao Zou , Xiaoqiang Wang , Lielin Wang , Ning Pan , Fang Xiang","doi":"10.1016/j.comptc.2024.114952","DOIUrl":"10.1016/j.comptc.2024.114952","url":null,"abstract":"<div><div>The present work investigated the adsorption of gaseous iodine molecules (I<sub>2</sub>) on stable CuS surface, which has demonstrated excellent performance as an adsorbent for I<sub>2</sub> removal, with first-principles density functional theory (DFT). In this work, a pair of asymmetric surfaces (marked as slab1 and slab2) formed by breaking the weakest bond along (0<!--> <!-->0<!--> <!-->1) direction are chosen to present CuS surfaces. The findings indicate that the adsorption of I<sub>2</sub> molecules on the pristine CuS(0<!--> <!-->0<!--> <!-->1) surface is relatively weak, while surface defects significantly enhance the binding strength of I<sub>2</sub>. In particular, S-vacancy CuS(0<!--> <!-->0<!--> <!-->1) surfaces exhibit considerably higher adsorption energy for I<sub>2</sub> compared to Cu-vacancy surfaces. We found that the hollow and Cu-top sites are typically the dominant adsorption sites, and the initial orientation of I<sub>2</sub> relative to the surface also influences the adsorption performance.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114952"},"PeriodicalIF":3.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593356","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 : 2024-10-30DOI: 10.1016/j.comptc.2024.114954
Muzzakkir Amin, Mohammad Musfiqur Rahman, Md Kazi Rokunuzzaman, Md Kamal Hossain, Farid Ahmed
Aromatic molecules exhibit strong non-covalent interactions with nanotubes, influencing their encapsulation properties. This study uses DFT calculations to explore the encapsulation of aromatic amino acids within zigzag (ZZ), chiral (R/S), and armchair (AC) single-walled aluminum nitride nanotubes (AlNNTs) and boron nitride nanotubes (BNNTs). The results reveal that zigzag AlNNTs exhibit the highest encapsulation affinity compared to other chiralities, while chiral BNNTs show enhanced encapsulation. Encapsulation energy decreases with increasing nanotube radius, indicating reduced affinity. Overall, the studied BNNTs demonstrate stronger encapsulation energy compared to AlNNTs. The bandgap energy of the encapsulated structures varies significantly with nanotube diameter and chirality. The physisorption process plays a major role in encapsulation, affecting the geometric and electronic properties of the nanotubes and enhancing the stability and efficacy of the encapsulated amino acids. These findings highlight the potential of these nanostructures for advanced applications, including targeted drug delivery and molecular sensing.
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Pub Date : 2024-10-30DOI: 10.1016/j.comptc.2024.114953
Miso Kim, Bonggeun Shong
Group 13 precursors play a pivotal role in thin-film deposition processes such as atomic layer deposition (ALD) and chemical vapor deposition (CVD), which are essential for semiconductor and nanomaterial applications. However, their strong tendency to dimerize complicates interfacial interactions, challenging precise control over deposition processes. Current study investigates the dimerization tendencies of group 13 precursors using density functional theory (DFT) calculations. It was revealed that dimerization energies follow the trend Al > In ≈ Ga ≫ B, and alkoxy > amido > halogen > alkyl, so that Al- and alkoxy-based precursors would exhibit the highest propensity for dimerization. Our analysis demonstrates that dimerization energies strongly correlate with key properties of the monomer precursors, particularly the partial charge on the central atom and the covalency of the central element-ligand bonds. Monomeric fractions for group 13 precursors under deposition process conditions offer detailed insights into their dimerization behavior.
13 族前驱体在原子层沉积 (ALD) 和化学气相沉积 (CVD) 等薄膜沉积过程中发挥着举足轻重的作用，对于半导体和纳米材料的应用至关重要。然而，它们强烈的二聚化倾向使界面相互作用变得复杂，给沉积过程的精确控制带来了挑战。本研究利用密度泛函理论（DFT）计算研究了 13 族前驱体的二聚化倾向。结果表明，二聚化能遵循 Al > In ≈ Ga ≫ B 和烷氧基 > 氨基 > 卤素 > 烷基的趋势，因此铝基和烷氧基基前体会表现出最高的二聚化倾向。我们的分析表明，二聚化能与单体前体的关键特性密切相关，特别是中心原子上的部分电荷和中心元素-配体键的共价性。在沉积工艺条件下，13 族前体的单体馏分提供了对其二聚化行为的详细了解。
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