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.
{"title":"First-principles study of aromatic amino acid encapsulation in single-walled BN and AlN nanotubes","authors":"Muzzakkir Amin, Mohammad Musfiqur Rahman, Md Kazi Rokunuzzaman, Md Kamal Hossain, Farid Ahmed","doi":"10.1016/j.comptc.2024.114954","DOIUrl":"10.1016/j.comptc.2024.114954","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114954"},"PeriodicalIF":3.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657630","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.2024.114953
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。
{"title":"Dimerization equilibrium of group 13 precursors for vapor deposition of thin films","authors":"Miso Kim, Bonggeun Shong","doi":"10.1016/j.comptc.2024.114953","DOIUrl":"10.1016/j.comptc.2024.114953","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114953"},"PeriodicalIF":3.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142572997","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 aim of our study is to provide a possible insight into blue-shifting and red-shifting hydrogen bonding complexes. For that, we have taken CHX3 (X F, Cl, Br) with hydrogen bond acceptors such as H2O, HCl, HCN, C2H2, NH3, H2S, PH3, CH3OH, C6H6 (Y O, N, Cl, P, S, ). In this work, we have optimized and computed the vibrational frequency by performing quantum chemical calculations on the systems utilizing B3LYP and MP2 levels of theory with 6-311++G(d, p) and aug-cc-pVDZ basis sets. Further, we compared the various calculated findings, such as geometrical parameters, interaction energies (E), hyper-conjugative interactions, second-order perturbation energies (E2), Laplacian electron densities () at the intermolecular bond critical point (BCP), vibrational shift (). The dependence of vibrational frequency on bond length and Mulliken charge was studied. Since NH3 has a highly negative Mulliken charge, it attracts the hydrogen (H) of CH having a positive Mulliken charge. This effect weakens the CH bond, leading to a red shift in the stretching frequency. In these complexes, NBO analysis revealed a higher value of second-order perturbation as a result of hyper-conjugative interaction from Lewis base to (CH), thus a higher redshift is observed.
{"title":"Comparative analysis of red and blue-shifting hydrogen bonds in 1:1 haloform complexes","authors":"Giridhar Baburao, Aishwaryavela Esakkimuthu, Gopi Ragupathy","doi":"10.1016/j.comptc.2024.114935","DOIUrl":"10.1016/j.comptc.2024.114935","url":null,"abstract":"<div><div>The aim of our study is to provide a possible insight into blue-shifting and red-shifting hydrogen bonding complexes. For that, we have taken CHX<sub>3</sub> (X <span><math><mo>=</mo></math></span> F, Cl, Br) with hydrogen bond acceptors such as H<sub>2</sub>O, HCl, HCN, C<sub>2</sub>H<sub>2</sub>, NH<sub>3</sub>, H<sub>2</sub>S, PH<sub>3</sub>, CH<sub>3</sub>OH, C<sub>6</sub>H<sub>6</sub> (Y <span><math><mo>=</mo></math></span> O, N, Cl, P, S, <span><math><mi>π</mi></math></span>). In this work, we have optimized and computed the vibrational frequency by performing quantum chemical calculations on the systems utilizing B3LYP and MP2 levels of theory with 6-311++G(d, p) and aug-cc-pVDZ basis sets. Further, we compared the various calculated findings, such as geometrical parameters, interaction energies (<span><math><mi>Δ</mi></math></span>E), hyper-conjugative interactions, second-order perturbation energies (E<sub>2</sub>), Laplacian electron densities (<span><math><mrow><msup><mrow><mo>∇</mo></mrow><mrow><mn>2</mn></mrow></msup><mi>ρ</mi></mrow></math></span>) at the intermolecular bond critical point (BCP), vibrational shift (<span><math><mrow><mi>Δ</mi><mi>ν</mi></mrow></math></span>). The dependence of vibrational frequency on bond length and Mulliken charge was studied. Since NH<sub>3</sub> has a highly negative Mulliken charge, it attracts the hydrogen (H) of C<img>H having a positive Mulliken charge. This effect weakens the C<img>H bond, leading to a red shift in the stretching frequency. In these complexes, NBO analysis revealed a higher value of second-order perturbation as a result of hyper-conjugative interaction from Lewis base to <span><math><msup><mrow><mi>σ</mi></mrow><mrow><mo>∗</mo></mrow></msup></math></span>(C<img>H), thus a higher redshift is observed.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114935"},"PeriodicalIF":3.0,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142587481","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 : 2024-10-28DOI: 10.1016/j.comptc.2024.114943
Abdesslem Jedidi , Yasir Alzahrani , Saadullah G. Aziz , Osman I. Osman , Shaaban A. Elroby , Walid M.I. Hassan , Kamal A. Soliman
We used pentagonal boron nitride penta-BN2 (p-BN2) surface as a challenging material for the application as a gas sensor. The effect of applying a dopant on the surface was also studied, alongside the effect of decoration with a non-noble metal. Density Functional Theory (DFT) calculations were used to investigate the geometrical and electronic structures of the adsorbed H2S and SO2 gases on pristine (p-BN2) and doped carbon. They showed easy desorption processes from pristine surface and lead to high detection rates. This indicates that these surfaces are suitable for being used as sensors for H2S and SO2 gases. Additionally, pristine was decorated with nickel (Ni), iron (Fe), and cobalt (Co). The adsorption energies of the gases on the decorated metal pristine and their electronic properties were also performed. The results showed stronger adsorptions (chemisorption); that is, the charge transfers between the gas and the surface was considerably increased. These surfaces are, hence, more suitable for gases capture and removal by decomposition.
{"title":"The role of carbon doped and non-noble metal decorated p-BN2 for the adsorption of H2S and SO2 gases","authors":"Abdesslem Jedidi , Yasir Alzahrani , Saadullah G. Aziz , Osman I. Osman , Shaaban A. Elroby , Walid M.I. Hassan , Kamal A. Soliman","doi":"10.1016/j.comptc.2024.114943","DOIUrl":"10.1016/j.comptc.2024.114943","url":null,"abstract":"<div><div>We used pentagonal boron nitride penta-BN<sub>2</sub> (p-BN<sub>2</sub>) surface as a challenging material for the application as a gas sensor. The effect of applying a dopant on the surface was also studied, alongside the effect of decoration with a non-noble metal. Density Functional Theory (DFT) calculations were used to investigate the geometrical and electronic structures of the adsorbed H<sub>2</sub>S and SO<sub>2</sub> gases on pristine (p-BN<sub>2</sub>) and doped carbon. They showed easy desorption processes from pristine surface and lead to high detection rates. This indicates that these surfaces are suitable for being used as sensors for H<sub>2</sub>S and SO<sub>2</sub> gases. Additionally, pristine was decorated with nickel (Ni), iron (Fe), and cobalt (Co). The adsorption energies of the gases on the decorated metal pristine and their electronic properties were also performed. The results showed stronger adsorptions (chemisorption); that is, the charge transfers between the gas and the surface was considerably increased. These surfaces are, hence, more suitable for gases capture and removal by decomposition.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114943"},"PeriodicalIF":3.0,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142572996","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 : 2024-10-28DOI: 10.1016/j.comptc.2024.114941
M. Kashif Masood , Wahidullah Khan , Shumaila Bibi , Niqab Khan , Redi Kristian Pingak , Kamran Tahir , Javed Rehman , Aboud Ahmed Awadh Bahajjaj
Perovskite hydrides are promising materials for hydrogen capacity application to achieve the US DOE on-board criteria. We have investigated novel perovskite hydrides XZrH3 (X: Mg/Ca/Sr/Ba) for H2 storage and transportation applications. In this study we investigates the physical properties of XZrH3 light materials for solid-state hydrogen storage application by incorporating the DFT framework with the CASTEP code. We have theoretically examined the structural, mechanical, electronic, optical, and hydrogen storage properties of these materials. The selected compounds were fully relaxed and optimized in the cubic phase space group Pm-3 m. Structural phase stability was confirmed through thermodynamic, and mechanical analyses. Mechanical properties, evaluated based on Poisson’s ratio, the Puagh’s ratio, and Cauchy pressure, indicate the ductile behavior with a preference for ionic bonding. The electronic structure analysis reveals the metallic behavior of these materials. Optical calculations were also performed to provide additional insights into the physical properties of H2 compounds. The gravimetric hydrogen storage capacities were calculated as 2.55, 2.25, 1.66, and 1.31 wt% for MgZrH3, CaZrH3, SrZrH3, And BaZrH3 hydrides respectively. The identified properties of XZrH3 suggest that these materials could significantly enhance hydrogen storage systems, with potential integration into existing energy technologies, offering a pathway toward more efficient and sustainable hydrogen-based solutions.
{"title":"The structural, elastic, optoelectronic properties and hydrogen storage capability of lead-free hydrides XZrH3 (X: Mg/Ca/Sr/Ba) for hydrogen storage application: A DFT study","authors":"M. Kashif Masood , Wahidullah Khan , Shumaila Bibi , Niqab Khan , Redi Kristian Pingak , Kamran Tahir , Javed Rehman , Aboud Ahmed Awadh Bahajjaj","doi":"10.1016/j.comptc.2024.114941","DOIUrl":"10.1016/j.comptc.2024.114941","url":null,"abstract":"<div><div>Perovskite hydrides are promising materials for hydrogen capacity application to achieve the US DOE on-board criteria. We have investigated novel perovskite hydrides XZrH<sub>3</sub> (X: Mg/Ca/Sr/Ba) for H<sub>2</sub> storage and transportation applications. In this study we investigates the physical properties of XZrH<sub>3</sub> light materials for solid-state hydrogen storage application by incorporating the DFT framework with the CASTEP code. We have theoretically examined the structural, mechanical, electronic, optical, and hydrogen storage properties of these materials. The selected compounds were fully relaxed and optimized in the cubic phase space group <em>Pm</em>-3 m. Structural phase stability was confirmed through thermodynamic, and mechanical analyses. Mechanical properties, evaluated based on Poisson’s ratio, the Puagh’s ratio, and Cauchy pressure, indicate the ductile behavior with a preference for ionic bonding. The electronic structure analysis reveals the metallic behavior of these materials. Optical calculations were also performed to provide additional insights into the physical properties of H<sub>2</sub> compounds. The gravimetric hydrogen storage capacities were calculated as 2.55, 2.25, 1.66, and 1.31 wt% for MgZrH<sub>3</sub>, CaZrH<sub>3</sub>, SrZrH<sub>3</sub>, And BaZrH<sub>3</sub> hydrides respectively. The identified properties of XZrH<sub>3</sub> suggest that these materials could significantly enhance hydrogen storage systems, with potential integration into existing energy technologies, offering a pathway toward more efficient and sustainable hydrogen-based solutions.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114941"},"PeriodicalIF":3.0,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561276","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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