Pub Date : 2024-10-20DOI: 10.1016/j.comptc.2024.114922
Jungwon Yun , Seongjun Lee , Dasol Bae , Minkyu Kim
This study investigates the oxidative coupling of methane on the IrO2(1 1 0) surface using TPRS simulations informed by DFT-derived data. We discover that the efficiency of the IrO2(1 1 0) surface in generating ethylene is strongly influenced by methane surface coverage. Our simulations reveal that the presence of surface hydroxyl group enhances the yield of C2+ species from methane oxidation, but this effect is counteracted at high methane coverages due to the accelerated formation of CH2OH. In addition, the study reveals that slight modifications in energy barriers at the branching point (C2H4 formation vs. CH2OH formation) significantly affect C2H4(g) production from the simulation, underscoring the importance of precise energetic data for accurate catalytic reaction predictions. The results have broader implications for reactions and catalysts where branching point selectivity determines high-value product yields. Thus, combining surface science with computational analysis is crucial for accurately determining energy profiles of key steps at the branching points.
{"title":"Intrinsic reactivity of stoichiometric IrO2(1 1 0) surface toward oxidative coupling of methane","authors":"Jungwon Yun , Seongjun Lee , Dasol Bae , Minkyu Kim","doi":"10.1016/j.comptc.2024.114922","DOIUrl":"10.1016/j.comptc.2024.114922","url":null,"abstract":"<div><div>This study investigates the oxidative coupling of methane on the IrO<sub>2</sub>(1<!--> <!-->1<!--> <!-->0) surface using TPRS simulations informed by DFT-derived data. We discover that the efficiency of the IrO<sub>2</sub>(1<!--> <!-->1<!--> <!-->0) surface in generating ethylene is strongly influenced by methane surface coverage. Our simulations reveal that the presence of surface hydroxyl group enhances the yield of C<sub>2</sub>+ species from methane oxidation, but this effect is counteracted at high methane coverages due to the accelerated formation of CH<sub>2</sub>OH. In addition, the study reveals that slight modifications in energy barriers at the branching point (C<sub>2</sub>H<sub>4</sub> formation vs. CH<sub>2</sub>OH formation) significantly affect C<sub>2</sub>H<sub>4</sub>(g) production from the simulation, underscoring the importance of precise energetic data for accurate catalytic reaction predictions. The results have broader implications for reactions and catalysts where branching point selectivity determines high-value product yields. Thus, combining surface science with computational analysis is crucial for accurately determining energy profiles of key steps at the branching points.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114922"},"PeriodicalIF":3.0,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529106","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 : 2024-10-19DOI: 10.1016/j.comptc.2024.114924
Kui Yuan, Hao-Ran Yang, Yang Wang
The mechanism and role of catalyst on the PPh3-catalyzed [4 + 3] annulation reaction have been systematically investigated using density functional theory (DFT) method. Based on the calculations, the possible mechanism contains six steps: nucleophilic addition of PPh3 to allenoate to give Z-configured intermediate, cleavage of CO bond for forming phosphonium diene, nucleophilic addition of phosphonium diene with anionic 1C,3N-dinucleophile, intramolecular [1], [5]-proton shift, ring-closure, and dissociation of catalyst. Non-covalent interaction (NCI) analysis shows that the O⋯P interaction would be the key for leading to the Z-configured pathway more favorable and electron localization function (ELF) analysis indicates that the implication of PPh3 can significantly lower the energy barrier involved in CO cleavage process, which mainly because the addition of PPh3 reduces the electron density of CO bond and thus facilities the cleavage of CO bond. This theoretical study would provide some clues for understanding the role of catalyst in a catalytic reaction.
利用密度泛函理论（DFT）方法系统地研究了 PPh3 催化[4 + 3]环化反应的机理和催化剂的作用。根据计算结果，可能的机理包括六个步骤：PPh3 与烯酸酯发生亲核加成反应，得到 Z 构型中间体；裂解 CO 键形成二烯膦；二烯膦与阴离子 1C,3N-亲核物发生亲核加成反应；分子内 [1]、[5]- 质子移动；闭环；催化剂解离。非共价相互作用（NCI）分析表明，O⋯P 相互作用是导致 Z 构型途径更有利的关键，而电子定位功能（ELF）分析表明，PPh3 的加入能显著降低 CO 裂解过程的能障，这主要是因为 PPh3 的加入降低了 CO 键的电子密度，从而促进了 CO 键的裂解。这项理论研究将为理解催化剂在催化反应中的作用提供一些线索。
{"title":"Mechanistic studies on phosphine-catalyzed [4 + 3] annulation of β′-acetoxy allenoate with 1C,3N-dinucleophile","authors":"Kui Yuan, Hao-Ran Yang, Yang Wang","doi":"10.1016/j.comptc.2024.114924","DOIUrl":"10.1016/j.comptc.2024.114924","url":null,"abstract":"<div><div>The mechanism and role of catalyst on the PPh<sub>3</sub>-catalyzed [4 + 3] annulation reaction have been systematically investigated using density functional theory (DFT) method. Based on the calculations, the possible mechanism contains six steps: nucleophilic addition of PPh<sub>3</sub> to allenoate to give Z-configured intermediate, cleavage of C<img>O bond for forming phosphonium diene, nucleophilic addition of phosphonium diene with anionic 1C,3N-dinucleophile, intramolecular <span><span>[1]</span></span>, <span><span>[5]</span></span>-proton shift, ring-closure, and dissociation of catalyst. Non-covalent interaction (NCI) analysis shows that the O<strong>⋯</strong>P interaction would be the key for leading to the Z-configured pathway more favorable and electron localization function (ELF) analysis indicates that the implication of PPh<sub>3</sub> can significantly lower the energy barrier involved in C<img>O cleavage process, which mainly because the addition of PPh<sub>3</sub> reduces the electron density of C<img>O bond and thus facilities the cleavage of C<img>O bond. This theoretical study would provide some clues for understanding the role of catalyst in a catalytic reaction.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114924"},"PeriodicalIF":3.0,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529113","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 : 2024-10-18DOI: 10.1016/j.comptc.2024.114916
B. Mouhib , S. Dahbi , N. Baaalla , N. Tahiri , O. El Bounagui , A. El Mansouri , H. Ez-Zahraouy
This study aims to explore the electronic structure, thermodynamic, mechanical stability, and optical response of Iodine-based ordered vacancy double halide perovskite compounds through the application of density functional theory. The two compounds Cs2ZrI6 and Rb2ZrI6 exhibit thermodynamic stability, with displaying particularly notable. Moreover, analysis of the calculated coefficients of elastic stiffness confirms the mechanical stability of all materials under ambient pressure conditions. By using the Density Functional Theory with Spin-Orbit Coupling (SOC), it was observed that Cs2TeI6 and Rb2TeI6 possess an indirect band gap located between the X and L high-symmetry points, this show that Cs2TeI6, Rb2ZrI6, Cs2HfI6, and Rb2HfI6 are identified as direct semiconductor compounds. Moreover, the band gap values of X2YI6 (where X = Cs, Rb, and Y = Te, Zr, and Hf) exhibit an increasing trend as we progress along the alkali and transition metal elements in the periodic table, ranging from 1.422 eV for Cs2TeI6 to 2.465 eV for Rb2TeI6. Besides, the optical behavior of the visible light show that X2YI6 compounds have a high absorption of about 70%, reflectance of 30%, and a low transmittance. Thanks to their advantageous bandgap, enduring stabilities, and effective absorption of visible light, Cs2TeI6 and Rb2TeI6 hold significant promise for a wide range of electronic and optoelectronic applications, particularly in photovoltaics.
{"title":"A comprehensive DFT Study of the electronic structure and optical properties of Iodine-based halide double perovskites for photovoltaic applications","authors":"B. Mouhib , S. Dahbi , N. Baaalla , N. Tahiri , O. El Bounagui , A. El Mansouri , H. Ez-Zahraouy","doi":"10.1016/j.comptc.2024.114916","DOIUrl":"10.1016/j.comptc.2024.114916","url":null,"abstract":"<div><div>This study aims to explore the electronic structure, thermodynamic, mechanical stability, and optical response of Iodine-based ordered vacancy double halide perovskite compounds through the application of density functional theory. The two compounds Cs<sub>2</sub>ZrI<sub>6</sub> and Rb<sub>2</sub>ZrI<sub>6</sub> exhibit thermodynamic stability, with displaying particularly notable. Moreover, analysis of the calculated coefficients of elastic stiffness confirms the mechanical stability of all materials under ambient pressure conditions. By using the Density Functional Theory with Spin-Orbit Coupling (SOC), it was observed that Cs2TeI6 and Rb2TeI6 possess an indirect band gap located between the X and L high-symmetry points, this show that Cs<sub>2</sub>TeI<sub>6</sub>, Rb<sub>2</sub>ZrI<sub>6</sub>, Cs<sub>2</sub>HfI<sub>6</sub>, and Rb<sub>2</sub>HfI<sub>6</sub> are identified as direct semiconductor compounds. Moreover, the band gap values of X<sub>2</sub>YI<sub>6</sub> (where X = Cs, Rb, and Y = Te, Zr, and Hf) exhibit an increasing trend as we progress along the alkali and transition metal elements in the periodic table, ranging from 1.422 eV for Cs<sub>2</sub>TeI<sub>6</sub> to 2.465 eV for Rb<sub>2</sub>TeI<sub>6</sub>. Besides, the optical behavior of the visible light show that X<sub>2</sub>YI<sub>6</sub> compounds have a high absorption of about 70%, reflectance of 30%, and a low transmittance. Thanks to their advantageous bandgap, enduring stabilities, and effective absorption of visible light, Cs<sub>2</sub>TeI<sub>6</sub> and Rb<sub>2</sub>TeI<sub>6</sub> hold significant promise for a wide range of electronic and optoelectronic applications, particularly in photovoltaics.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114916"},"PeriodicalIF":3.0,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529107","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 : 2024-10-18DOI: 10.1016/j.comptc.2024.114929
Yu-Pu He , Tian-Hao Guo , Shao-Yi Wu , Shi-Yu Zuo , Jun-Chao Fu , Xiao-Yu Li
It is crucial to develop highly efficient, selective and low-overpotential electrocatalysts for CO2 reduction. This paper proposes an efficient iron and nickel single-atom catalyst using Janus MoSSe as the substrate to reduce CO2 to CO by using DFT calculations. The adsorption of a single TM atom like Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt on Janus MoSSe monolayer results in a decrease in band gap, which may accelerate the catalytic CO2 reduction. The excellent catalytic activity of Fe@MoSSe and Ni@MoSSe is owing to the high d-band center and hence the strong TM-CO2 bonding. The asymmetric structure of Janus MoSSe creates the local built-in electric field, which further increases by about 8% or 0.8% after the adsorption of single Ni or Fe atom so as to afford the better electrocatalytic performances for reduction of CO2 to CO in both TM modified systems. So, this work proposes the catalysts Fe@MoSSe and Ni@MoSSe with good selectivity and activity for CO2 reduction by revealing their underlying mechanisms, and Janus MoSSe may be used as a potential substrate material for CO2 reduction catalysts.
开发高效、高选择性和低过电位的二氧化碳还原电催化剂至关重要。本文通过 DFT 计算，提出了一种以 Janus MoSSe 为底物的高效铁镍单原子催化剂，用于将 CO2 还原为 CO。在 Janus MoSSe 单层上吸附 Fe、Co、Ni、Ru、Rh、Pd、Os、Ir 和 Pt 等单个 TM 原子会导致带隙减小，从而加速催化 CO2 还原。Fe@MoSSe和Ni@MoSSe之所以具有出色的催化活性，是因为它们具有较高的d带中心，因而具有较强的TM-CO2键。Janus MoSSe 的不对称结构产生了局部内置电场，在吸附单个 Ni 或 Fe 原子后，电场进一步增加了约 8%或 0.8%，从而使这两种 TM 修饰体系在将 CO2 还原成 CO 时具有更好的电催化性能。因此，本研究通过揭示Fe@MoSSe和Ni@MoSSe的内在机理，提出了具有良好选择性和活性的CO2还原催化剂，Janus MoSSe可作为CO2还原催化剂的潜在基底材料。
{"title":"TM@MoSSe (TM = Ni, Fe) as novel electrocatalysts for reduction of CO2 to CO: A DFT study","authors":"Yu-Pu He , Tian-Hao Guo , Shao-Yi Wu , Shi-Yu Zuo , Jun-Chao Fu , Xiao-Yu Li","doi":"10.1016/j.comptc.2024.114929","DOIUrl":"10.1016/j.comptc.2024.114929","url":null,"abstract":"<div><div>It is crucial to develop highly efficient, selective and low-overpotential electrocatalysts for CO<sub>2</sub> reduction. This paper proposes an efficient iron and nickel single-atom catalyst using Janus MoSSe as the substrate to reduce CO<sub>2</sub> to CO by using DFT calculations. The adsorption of a single TM atom like Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt on Janus MoSSe monolayer results in a decrease in band gap, which may accelerate the catalytic CO<sub>2</sub> reduction. The excellent catalytic activity of Fe@MoSSe and Ni@MoSSe is owing to the high <em>d</em>-band center and hence the strong TM-CO<sub>2</sub> bonding. The asymmetric structure of Janus MoSSe creates the local built-in electric field, which further increases by about 8% or 0.8% after the adsorption of single Ni or Fe atom so as to afford the better electrocatalytic performances for reduction of CO<sub>2</sub> to CO in both TM modified systems. So, this work proposes the catalysts Fe@MoSSe and Ni@MoSSe with good selectivity and activity for CO<sub>2</sub> reduction by revealing their underlying mechanisms, and Janus MoSSe may be used as a potential substrate material for CO<sub>2</sub> reduction catalysts.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114929"},"PeriodicalIF":3.0,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529116","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 : 2024-10-18DOI: 10.1016/j.comptc.2024.114930
Lin Li , Xiaolu Xiong , Jian-Qiang Wang
Pr(Ba,Sr)Co2O5+δ is a promising cathode material for solid oxide fuel cell (SOFC) due to its high oxygen ion transport capability and oxygen reduction activity. Density functional theory (DFT) calculations were performed to elucidate the oxygen reduction mechanism of B-site doped Pr(Ba,Sr)(Co,M)2O5+δ (M = Fe, Ni, Cu, and Zn) materials. First, we investigated the formation of O vacancies. The results indicate that Cu and Zn doping facilitate O vacancy formation, resulting in lower O vacancy formation energies. Furthermore, the interaction between oxygen and the (0 0 1) surfaces of B-site doped Pr(Ba,Sr)(Co,M)2O5+δ has been comprehensively discussed, involving both perfect and defective surfaces. The results demonstrate that the presence of O vacancies enhances the catalytic activity for oxygen reduction, by reducing the energy required for O2 dissociation. Zn-doped Pr(Ba,Sr)(Co,M)2O5+δ exhibits a low O vacancy formation energy, resulting in a stable adsorption configuration upon oxygen dissociation, indicating its potential as a cathode material for SOFC.
Pr(Ba,Sr)Co2O5+δ具有很高的氧离子传输能力和氧还原活性，是一种很有前途的固体氧化物燃料电池（SOFC）阴极材料。为了阐明 B 位掺杂 Pr(Ba,Sr)(Co,M)2O5+δ（M = Fe、Ni、Cu 和 Zn）材料的氧还原机制，我们进行了密度泛函理论（DFT）计算。首先，我们研究了 O 空位的形成。结果表明，Cu 和 Zn 的掺杂促进了 O 空位的形成，从而降低了 O 空位的形成能。此外，我们还全面讨论了氧与 B 位掺杂的 Pr(Ba,Sr)(Co,M)2O5+δ（0 0 1）表面之间的相互作用，包括完美表面和缺陷表面。结果表明，O 空位的存在可降低 O2 解离所需的能量，从而增强氧还原的催化活性。掺锌的 Pr(Ba,Sr)(Co,M)2O5+δ具有较低的 O 空位形成能，从而在氧气解离时形成稳定的吸附构型，这表明它具有作为 SOFC 阴极材料的潜力。
{"title":"Atomic-scale mechanistic study of oxygen reduction mechanism for B-site doped Pr(Ba,Sr)Co2O5+δ by density functional theory calculations","authors":"Lin Li , Xiaolu Xiong , Jian-Qiang Wang","doi":"10.1016/j.comptc.2024.114930","DOIUrl":"10.1016/j.comptc.2024.114930","url":null,"abstract":"<div><div>Pr(Ba,Sr)Co<sub>2</sub>O<sub>5+δ</sub> is a promising cathode material for solid oxide fuel cell (SOFC) due to its high oxygen ion transport capability and oxygen reduction activity. Density functional theory (DFT) calculations were performed to elucidate the oxygen reduction mechanism of B-site doped Pr(Ba,Sr)(Co,M)<sub>2</sub>O<sub>5+δ</sub> (M = Fe, Ni, Cu, and Zn) materials. First, we investigated the formation of O vacancies. The results indicate that Cu and Zn doping facilitate O vacancy formation, resulting in lower O vacancy formation energies. Furthermore, the interaction between oxygen and the (0 0 1) surfaces of B-site doped Pr(Ba,Sr)(Co,M)<sub>2</sub>O<sub>5+δ</sub> has been comprehensively discussed, involving both perfect and defective surfaces. The results demonstrate that the presence of O vacancies enhances the catalytic activity for oxygen reduction, by reducing the energy required for O<sub>2</sub> dissociation. Zn-doped Pr(Ba,Sr)(Co,M)<sub>2</sub>O<sub>5+δ</sub> exhibits a low O vacancy formation energy, resulting in a stable adsorption configuration upon oxygen dissociation, indicating its potential as a cathode material for SOFC.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114930"},"PeriodicalIF":3.0,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529103","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 : 2024-10-18DOI: 10.1016/j.comptc.2024.114917
Farag M.A. Altalbawy , Safaa Mustafa Hameed , M.M. Rekha , Anurag Mishra , Shilpa Sharma , G.V. Siva Prasad , Iman Samir Alalaq , Ayadh Al-khalidi , Ahmed Ali Mtasher , Fadeel F. Seed
In this project, the possibility of removal of copper (elemental Cu (0) and Cu (I) ion) from the environment by applying some heteroatom decorated graphitic carbonitride (g-C3N4) nanosheets has been investigated. Due to the recent reports about the toxicity of Cu overload and its intervention in a wide range of health problems such as Wilson’s disease (Cu overload), elimination of this element from the environment is important (in view of medicinal chemistry and health science). Thus, this research has focused on the investigations that are related to the possibility of removal of Cu ions from the environment (applying the g-C3N4 nanosheet and its derivatives). The results have shown that the g-C3N4N is the strongest nanosheet for adsorption and removal of both Cu (0) atom, and Cu (I) ion. In addition, in view of sensing abilities, the results have indicated that the best sensor (having the ability of recognition of Cu (0) atom from Cu (I) ion, is C3N4O.
在该项目中，研究人员利用一些杂原子装饰的石墨碳氮化物（g-C3N4）纳米片，研究了从环境中去除铜（元素 Cu (0) 和 Cu (I) 离子）的可能性。由于最近有关铜超载的毒性及其在威尔逊氏病（铜超载）等多种健康问题中的干预作用的报道，从环境中消除这种元素非常重要（从药物化学和健康科学的角度来看）。因此，本研究重点研究了从环境中去除铜离子的可能性（应用 g-C3N4 纳米片及其衍生物）。结果表明，g-C3N4N 是吸附和去除 Cu (0) 原子和 Cu (I) 离子最强的纳米片。此外，在传感能力方面，结果表明 C3N4O 是最好的传感器（具有识别 Cu (0) 原子和 Cu (I) 离子的能力）。
{"title":"A theoretical approach on the removal of elemental Cu and Cu (I) ions applying the g-C3N4S, g-C3N4O, g-C3N4N, and g-C3N4 nanosheets","authors":"Farag M.A. Altalbawy , Safaa Mustafa Hameed , M.M. Rekha , Anurag Mishra , Shilpa Sharma , G.V. Siva Prasad , Iman Samir Alalaq , Ayadh Al-khalidi , Ahmed Ali Mtasher , Fadeel F. Seed","doi":"10.1016/j.comptc.2024.114917","DOIUrl":"10.1016/j.comptc.2024.114917","url":null,"abstract":"<div><div>In this project, the possibility of removal of copper (elemental Cu (0) and Cu (I) ion) from the environment by applying some heteroatom decorated graphitic carbonitride (g-C<sub>3</sub>N<sub>4</sub>) nanosheets has been investigated. Due to the recent reports about the toxicity of Cu overload and its intervention in a wide range of health problems such as Wilson’s disease (Cu overload), elimination of this element from the environment is important (in view of medicinal chemistry and health science). Thus, this research has focused on the investigations that are related to the possibility of removal of Cu ions from the environment (applying the g-C<sub>3</sub>N<sub>4</sub> nanosheet and its derivatives). The results have shown that the g-C<sub>3</sub>N<sub>4</sub>N is the strongest nanosheet for adsorption and removal of both Cu (0) atom, and Cu (I) ion. In addition, in view of sensing abilities, the results have indicated that the best sensor (having the ability of recognition of Cu (0) atom from Cu (I) ion, is C<sub>3</sub>N<sub>4</sub>O.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114917"},"PeriodicalIF":3.0,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529110","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 : 2024-10-18DOI: 10.1016/j.comptc.2024.114925
U.S. Okorie, G.J. Rampho
In this article, the asymptotic iteration method and the Laguerre polynomials are employed to obtain the eigensolutions of the Schrödinger equation with modified shifted Morse potential model. Vibrational energy results for sodium dimer have been presented numerically and these results are compared with experimental data from available literatures. With the help of the energy expression, the partition function and other thermodynamic function expressions of this potential model for sodium dimer are obtained, using the Euler MacLaurin’s formula. For various vibrational quantum numbers considered, the thermodynamic functions show high level of dependence on the temperature parameter. These results are justified by the numerical results presented for the thermodynamic functions of sodium dimer. Our results also agree with the available results in literatures and can also serve as a guiding reference in further studies concerning chemical physics and spectroscopy.
{"title":"Theoretical computation of thermodynamic functions of sodium dimer with modified shifted Morse potential","authors":"U.S. Okorie, G.J. Rampho","doi":"10.1016/j.comptc.2024.114925","DOIUrl":"10.1016/j.comptc.2024.114925","url":null,"abstract":"<div><div>In this article, the asymptotic iteration method and the Laguerre polynomials are employed to obtain the eigensolutions of the Schrödinger equation with modified shifted Morse potential model. Vibrational energy results for sodium dimer have been presented numerically and these results are compared with experimental data from available literatures. With the help of the energy expression, the partition function and other thermodynamic function expressions of this potential model for sodium dimer are obtained, using the Euler MacLaurin’s formula. For various vibrational quantum numbers considered, the thermodynamic functions show high level of dependence on the temperature parameter. These results are justified by the numerical results presented for the thermodynamic functions of sodium dimer. Our results also agree with the available results in literatures and can also serve as a guiding reference in further studies concerning chemical physics and spectroscopy.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114925"},"PeriodicalIF":3.0,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529644","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 study of nanomaterials with different sizes and shapes is of considerable recent interest. Polyhex carbon nanotubes form an important class of nanomaterials that find several applications. Topological properties and entropies of two phases of carbon nanotubes, namely the zigzag and armchair configurations, have been juxtaposed through the reverse degree-based topological indices. The entropies and topologies of the two phases of the carbon nanotubes are also computed and compared which reveal that the zigzag nanotubes exhibit greater entropies compared to the armchair nanotubes. Applications of the developed techniques to various spectroscopies including NMR and ESR spectroscopies, are also pointed out. In future studies, detailed analysis and applications of reverse, reduced reverse topological indices and entropy of various other complex chemical structures will be considered.
{"title":"Novel topological reverse indices and entropies of armchair versus zigzag polyhex carbon nanotubes with spectroscopic applications","authors":"Medha Itagi Huilgol , P.H. Shobha , Krishnan Balasubramanian","doi":"10.1016/j.comptc.2024.114921","DOIUrl":"10.1016/j.comptc.2024.114921","url":null,"abstract":"<div><div>The study of nanomaterials with different sizes and shapes is of considerable recent interest. Polyhex carbon nanotubes form an important class of nanomaterials that find several applications. Topological properties and entropies of two phases of carbon nanotubes, namely the zigzag and armchair configurations, have been juxtaposed through the reverse degree-based topological indices. The entropies and topologies of the two phases of the carbon nanotubes are also computed and compared which reveal that the zigzag nanotubes exhibit greater entropies compared to the armchair nanotubes. Applications of the developed techniques to various spectroscopies including NMR and ESR spectroscopies, are also pointed out. In future studies, detailed analysis and applications of reverse, reduced reverse topological indices and entropy of various other complex chemical structures will be considered.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1242 ","pages":"Article 114921"},"PeriodicalIF":3.0,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554746","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 : 2024-10-16DOI: 10.1016/j.comptc.2024.114904
Regina M. Burganova, Sadegh Kaviani, Irina I. Piyanzina, Oleg V. Nedopekin
A detailed density functional theory study was conducted on the nanocomposites formed by polyaniline and yttrium oxide clusters, employing the mixed 6-311G(d,p)/LANL2DZ basis set. The investigation identified the formation of the nanocomposites through strong covalent bonding and moderate electrostatic interactions, resulting in significant binding energies. These interactions contributed to a reduction in the band gap, increased electron activity, and higher chemical reactivity compared to pure polyaniline. The formation of the nanocomposites induced a redshift in the UV–vis absorption spectra, moving the maximum absorption wavelength from the ultraviolet to the visible region, indicating n-type doping. Natural bond orbital analysis confirmed the role of yttrium oxide clusters as electron acceptors, with polyaniline serving as an electron donor.
利用 6-311G(d,p)/LANL2DZ 混合基集对聚苯胺和氧化钇簇合物形成的纳米复合材料进行了详细的密度泛函理论研究。研究发现，纳米复合材料是通过强共价键和中等静电相互作用形成的，从而产生了显著的结合能。与纯聚苯胺相比，这些相互作用降低了带隙，增加了电子活性，提高了化学反应活性。纳米复合材料的形成引起了紫外-可见吸收光谱的重移，最大吸收波长从紫外区移到了可见区，这表明了 n 型掺杂。自然键轨道分析证实了氧化钇团簇作为电子受体的作用，而聚苯胺则是电子供体。
{"title":"Molecular design and characterization of the PANI/yttrium oxide multifunctional nanocomposite material","authors":"Regina M. Burganova, Sadegh Kaviani, Irina I. Piyanzina, Oleg V. Nedopekin","doi":"10.1016/j.comptc.2024.114904","DOIUrl":"10.1016/j.comptc.2024.114904","url":null,"abstract":"<div><div>A detailed density functional theory study was conducted on the nanocomposites formed by polyaniline and yttrium oxide clusters, employing the mixed 6-311G(d,p)/LANL2DZ basis set. The investigation identified the formation of the nanocomposites through strong covalent bonding and moderate electrostatic interactions, resulting in significant binding energies. These interactions contributed to a reduction in the band gap, increased electron activity, and higher chemical reactivity compared to pure polyaniline. The formation of the nanocomposites induced a redshift in the UV–vis absorption spectra, moving the maximum absorption wavelength from the ultraviolet to the visible region, indicating <em>n</em>-type doping. Natural bond orbital analysis confirmed the role of yttrium oxide clusters as electron acceptors, with polyaniline serving as an electron donor.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114904"},"PeriodicalIF":3.0,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529115","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 : 2024-10-15DOI: 10.1016/j.comptc.2024.114923
Zhiheng Yu , Yanli Li , Yanwei Wen , Bin Shan , Jiaqiang Yang
Hydrogen binding energy in metal materials is of high significance in the hydrogen storage as well as the hydrogen evolution reaction of electrocatalysis. In this work, the datasets (more than 9000 data) of hydrogen adsorbed on Pt nanoclusters with different sizes are obtained by first-principles calculations. Data analysis shows that the binding strength of hydrogen with Pt is closely relevant to the local structures of the adsorption sites. The local features of the distance between the platinum and hydrogen and the size of the nanoclusters are supplemented to the Smooth Overlap of Atomic Positions descriptors to fit and predict the adsorption energies of hydrogen on different Pt nano-structures by performing the machine learning method. Gaussian Process Regression (GPR) and Random Forest Regressor (RFR) are used to construct the prediction model of hydrogen binding energies and it is found the R2 of test set is improved from 0.63 to 0.78 with modified descriptors. By applying it into other nanoclusters, the MAE of the prediction model is 0.08 eV, which exhibits high accuracy of the hydrogen adsorption energy. Our model can be easily extended to the prediction of hydrogen adsorption energy of other materials with affordable computational cost and accuracy, which would be helpful for the structural design of high-performance catalysts.
{"title":"Machine learning prediction of hydrogen adsorption energy on platinum nanoclusters: A comparative study of SOAP descriptors","authors":"Zhiheng Yu , Yanli Li , Yanwei Wen , Bin Shan , Jiaqiang Yang","doi":"10.1016/j.comptc.2024.114923","DOIUrl":"10.1016/j.comptc.2024.114923","url":null,"abstract":"<div><div>Hydrogen binding energy in metal materials is of high significance in the hydrogen storage as well as the hydrogen evolution reaction of electrocatalysis. In this work, the datasets (more than 9000 data) of hydrogen adsorbed on Pt nanoclusters with different sizes are obtained by first-principles calculations. Data analysis shows that the binding strength of hydrogen with Pt is closely relevant to the local structures of the adsorption sites. The local features of the distance between the platinum and hydrogen and the size of the nanoclusters are supplemented to the Smooth Overlap of Atomic Positions descriptors to fit and predict the adsorption energies of hydrogen on different Pt nano-structures by performing the machine learning method. Gaussian Process Regression (GPR) and Random Forest Regressor (RFR) are used to construct the prediction model of hydrogen binding energies and it is found the R<sup>2</sup> of test set is improved from 0.63 to 0.78 with modified descriptors. By applying it into other nanoclusters, the MAE of the prediction model is 0.08 eV, which exhibits high accuracy of the hydrogen adsorption energy. Our model can be easily extended to the prediction of hydrogen adsorption energy of other materials with affordable computational cost and accuracy, which would be helpful for the structural design of high-performance catalysts.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1241 ","pages":"Article 114923"},"PeriodicalIF":3.0,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142529642","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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