Pub Date : 2025-02-14DOI: 10.1016/j.comptc.2025.115139
A.C.L. Moreira, J.A.B. Silva, A.J.L. Oliveira
In this work we propose a theoretical study of an interplay between impurities effects and transversal electric field (TEF) in charge transport through a two terminals device composed by a pure anthracene and a doped one. We use the Landauer approach, with the electronic structure treated at a density functional theory (DFT) level and model the self-energy with complex absorbing potentials. For the pure anthracene, the effect of the applied TEF is less significant than for the doped anthracene, where the dipole moment is high and the transverse field trends to rotate it. The changes in the geometry of the system alter the electronic structure in such manner that delocalized molecular orbitals can appear, thus opening transport channels. Our results reveal how the impurity on the anthracene island facilitates the control of the electrical current.
{"title":"Transverse electric field as a controller of the magnitude of electric current through a doped anthracene island","authors":"A.C.L. Moreira, J.A.B. Silva, A.J.L. Oliveira","doi":"10.1016/j.comptc.2025.115139","DOIUrl":"10.1016/j.comptc.2025.115139","url":null,"abstract":"<div><div>In this work we propose a theoretical study of an interplay between impurities effects and transversal electric field (TEF) in charge transport through a two terminals device composed by a pure anthracene and a doped one. We use the Landauer approach, with the electronic structure treated at a density functional theory (DFT) level and model the self-energy with complex absorbing potentials. For the pure anthracene, the effect of the applied TEF is less significant than for the doped anthracene, where the dipole moment is high and the transverse field trends to rotate it. The changes in the geometry of the system alter the electronic structure in such manner that delocalized molecular orbitals can appear, thus opening transport channels. Our results reveal how the impurity on the anthracene island facilitates the control of the electrical current.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115139"},"PeriodicalIF":3.0,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427597","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 : 2025-02-13DOI: 10.1016/j.comptc.2025.115124
Klinton Brito K. , Sudharsan J.B. , Srinivasan M. , Prammitha Rajaram , Prasath M. , Nivetha G.F.
<div><div>In this study, we investigate the spintronic and thermoelectric properties of half-Heusler alloys <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>Z</mi></mrow></math></span> (<span><math><mrow><mi>Z</mi><mo>=</mo><mi>S</mi><mi>n</mi><mo>,</mo><mi>S</mi><mi>b</mi><mo>,</mo><mi>B</mi><mi>i</mi></mrow></math></span>) using density functional theory. Initially, we have optimized the cubic structure of the considered crystal alloys for various magnetic phases. Through calculations, we obtained that minimum ground state energy in ferro-magnetic phase. Following we have confirmed both the structural and mechanical stability of the alloys. Using generalized gradient approximation, we studied the electronic properties of the alloys <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>Z</mi></mrow></math></span> (<span><math><mrow><mi>Z</mi><mo>=</mo><mi>S</mi><mi>n</mi><mo>,</mo><mi>S</mi><mi>b</mi><mo>,</mo><mi>B</mi><mi>i</mi></mrow></math></span>) and we obtained the band gap in spin up channel. For <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>S</mi><mi>n</mi></mrow></math></span>, the calculated band gap value is 0.77 eV, 1.09 eV for <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>S</mi><mi>b</mi></mrow></math></span> and the band gap value of <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>B</mi><mi>i</mi></mrow></math></span> is 0.29 eV in spin up channel. The presence of band gap only in the spin up channel confirms the half-metallic nature of the considered alloys. Also, the band gap are indirect in nature for <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>S</mi><mi>n</mi></mrow></math></span> and <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>S</mi><mi>b</mi></mrow></math></span> alloys whereas for <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>B</mi><mi>i</mi></mrow></math></span> the direct band gap is observed. The positive integer total magnetic moment values of <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>Z</mi></mrow></math></span> (<span><math><mrow><mi>Z</mi><mo>=</mo><mi>S</mi><mi>n</mi><mo>,</mo><mi>S</mi><mi>b</mi><mo>,</mo><mi>B</mi><mi>i</mi></mrow></math></span>) confirms the ferro magnetic nature of the materials. We have also studied the transport properties of the alloys <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>Z</mi></mrow></math></span> (<span><math><mrow><mi>Z</mi><mo>=</mo><mi>S</mi><mi>n</mi><mo>,</mo><mi>S</mi><mi>b</mi><mo>,</mo><mi>B</mi><mi>i</mi></mrow></math></span>) with the <span><math><mrow><mi>Z</mi><mi>T</mi></mrow></math></span> values 0.52, 0.6 and 0.29 respectively. Our results shows that the half-Heusler alloys <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>Z</mi></mrow></math></span> (<span><math><mrow><mi>Z</mi><mo>=</mo><mi>S</mi><mi>n</mi><mo>,</mo><mi>S</mi><mi>b</mi><mo>,</mo><mi>B</mi><mi>i</mi></mrow></math></span>) are suitable
{"title":"Hafnium based ferromagnetic half metals for spintronic and thermoelectric applications — Materials Computation","authors":"Klinton Brito K. , Sudharsan J.B. , Srinivasan M. , Prammitha Rajaram , Prasath M. , Nivetha G.F.","doi":"10.1016/j.comptc.2025.115124","DOIUrl":"10.1016/j.comptc.2025.115124","url":null,"abstract":"<div><div>In this study, we investigate the spintronic and thermoelectric properties of half-Heusler alloys <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>Z</mi></mrow></math></span> (<span><math><mrow><mi>Z</mi><mo>=</mo><mi>S</mi><mi>n</mi><mo>,</mo><mi>S</mi><mi>b</mi><mo>,</mo><mi>B</mi><mi>i</mi></mrow></math></span>) using density functional theory. Initially, we have optimized the cubic structure of the considered crystal alloys for various magnetic phases. Through calculations, we obtained that minimum ground state energy in ferro-magnetic phase. Following we have confirmed both the structural and mechanical stability of the alloys. Using generalized gradient approximation, we studied the electronic properties of the alloys <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>Z</mi></mrow></math></span> (<span><math><mrow><mi>Z</mi><mo>=</mo><mi>S</mi><mi>n</mi><mo>,</mo><mi>S</mi><mi>b</mi><mo>,</mo><mi>B</mi><mi>i</mi></mrow></math></span>) and we obtained the band gap in spin up channel. For <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>S</mi><mi>n</mi></mrow></math></span>, the calculated band gap value is 0.77 eV, 1.09 eV for <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>S</mi><mi>b</mi></mrow></math></span> and the band gap value of <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>B</mi><mi>i</mi></mrow></math></span> is 0.29 eV in spin up channel. The presence of band gap only in the spin up channel confirms the half-metallic nature of the considered alloys. Also, the band gap are indirect in nature for <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>S</mi><mi>n</mi></mrow></math></span> and <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>S</mi><mi>b</mi></mrow></math></span> alloys whereas for <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>B</mi><mi>i</mi></mrow></math></span> the direct band gap is observed. The positive integer total magnetic moment values of <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>Z</mi></mrow></math></span> (<span><math><mrow><mi>Z</mi><mo>=</mo><mi>S</mi><mi>n</mi><mo>,</mo><mi>S</mi><mi>b</mi><mo>,</mo><mi>B</mi><mi>i</mi></mrow></math></span>) confirms the ferro magnetic nature of the materials. We have also studied the transport properties of the alloys <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>Z</mi></mrow></math></span> (<span><math><mrow><mi>Z</mi><mo>=</mo><mi>S</mi><mi>n</mi><mo>,</mo><mi>S</mi><mi>b</mi><mo>,</mo><mi>B</mi><mi>i</mi></mrow></math></span>) with the <span><math><mrow><mi>Z</mi><mi>T</mi></mrow></math></span> values 0.52, 0.6 and 0.29 respectively. Our results shows that the half-Heusler alloys <span><math><mrow><mi>H</mi><mi>f</mi><mi>M</mi><mi>n</mi><mi>Z</mi></mrow></math></span> (<span><math><mrow><mi>Z</mi><mo>=</mo><mi>S</mi><mi>n</mi><mo>,</mo><mi>S</mi><mi>b</mi><mo>,</mo><mi>B</mi><mi>i</mi></mrow></math></span>) are suitable ","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115124"},"PeriodicalIF":3.0,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143403199","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 : 2025-02-13DOI: 10.1016/j.comptc.2025.115140
Arturo Elías-Domínguez, Dulce Y. Medina-Velázquez, Friné López-Medina, Fernando Pérez-Villaseñor, Ángel Castro-Agüero, Arturo Ortíz-Arroyo, Maria V. Hernandez-Ruiz
Liquid-liquid equilibrium (LLE) of two- and three-component systems containing short molecules has been previously studied by Monte Carlo simulations in the NPT ensemble with two simulation boxes; for systems with long-chain molecules have also been studied, but at low pressures and considering three simulation boxes, the third is a vapor phase that contains ghost molecules and acts only as a transfer medium between the two liquid phases. In this paper, the LLE at high pressures of the water/n-decane binary system is calculated using only two simulation boxes by the NPT-Gibbs ensemble combined with the Configurational Bias Monte Carlo method (CBMC). Besides, the molecular potential models used, and the simulation details allowed us to calculate the LLE properties of the system studied: the densities of the two phases in equilibrium, their compositions, and potential energies. The water/n-decane mixture is characterized by differences in molecular size and polarity, forming a highly non-ideal system. This is probably the reason for the difficulty of studying the LLE of water/n-alkane binary systems by Monte Carlo simulation, so to the best of our knowledge, this is the first study of the LLE of a binary water/n-alkane system using Monte Carlo simulation. Simulations were done at 573.2 K (from 121 to 303 bar) and 593.2 K (from 154 to 300 bar), and under these conditions, experimental data from the LLE is available, obtaining good predictions from simulations.
{"title":"Liquid-liquid equilibrium at high pressures of water/n-Decane system using Monte Carlo simulation","authors":"Arturo Elías-Domínguez, Dulce Y. Medina-Velázquez, Friné López-Medina, Fernando Pérez-Villaseñor, Ángel Castro-Agüero, Arturo Ortíz-Arroyo, Maria V. Hernandez-Ruiz","doi":"10.1016/j.comptc.2025.115140","DOIUrl":"10.1016/j.comptc.2025.115140","url":null,"abstract":"<div><div>Liquid-liquid equilibrium (LLE) of two- and three-component systems containing short molecules has been previously studied by Monte Carlo simulations in the NPT ensemble with two simulation boxes; for systems with long-chain molecules have also been studied, but at low pressures and considering three simulation boxes, the third is a vapor phase that contains ghost molecules and acts only as a transfer medium between the two liquid phases. In this paper, the LLE at high pressures of the water/n-decane binary system is calculated using only two simulation boxes by the NPT-Gibbs ensemble combined with the Configurational Bias Monte Carlo method (CBMC). Besides, the molecular potential models used, and the simulation details allowed us to calculate the LLE properties of the system studied: the densities of the two phases in equilibrium, their compositions, and potential energies. The water/n-decane mixture is characterized by differences in molecular size and polarity, forming a highly non-ideal system. This is probably the reason for the difficulty of studying the LLE of water/n-alkane binary systems by Monte Carlo simulation, so to the best of our knowledge, this is the first study of the LLE of a binary water/n-alkane system using Monte Carlo simulation. Simulations were done at 573.2 K (from 121 to 303 <em>bar</em>) and 593.2 <em>K</em> (from 154 to 300 <em>bar),</em> and under these conditions, experimental data from the LLE is available, obtaining good predictions from simulations.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115140"},"PeriodicalIF":3.0,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427598","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 : 2025-02-13DOI: 10.1016/j.comptc.2025.115141
Jonathan A. Da Silva , Gabriela Monteiro B. Da Silva , Roberta P. Dias , Augusto Cesar L. Moreira , Julio C.S. Da Silva
This study investigates graphene-based materials as potential candidates for molecular junction devices in thermoelectric applications. Using Density Functional Theory, Landauer-Büttiker scattering theory, and the complex absorbing potential technique, we examined molecular systems with pyrene as the conductive wire and graphene or aza-graphene as electrodes. The calculated conductance values (6.20 × 10−4 G₀ and 1.80 × 10−5 G₀ for graphene and aza-graphene systems, respectively) reveal a tenfold increase in the graphene system due to transport through the LUMO orbital. The thermoelectric power values (0.5–2.5 μV·K−1) were comparable to those of gold-based systems. Chemical modifications, such as the insertion of NO₂ into pyrene, further enhanced conductance. These findings underline the molecular structure's critical role in determining transport properties and place graphene-based systems as viable thermoelectric materials.
{"title":"Exploring thermoelectric conduction in new graphene-based molecular junctions dispositive: A computational perspective","authors":"Jonathan A. Da Silva , Gabriela Monteiro B. Da Silva , Roberta P. Dias , Augusto Cesar L. Moreira , Julio C.S. Da Silva","doi":"10.1016/j.comptc.2025.115141","DOIUrl":"10.1016/j.comptc.2025.115141","url":null,"abstract":"<div><div>This study investigates graphene-based materials as potential candidates for molecular junction devices in thermoelectric applications. Using Density Functional Theory, Landauer-Büttiker scattering theory, and the complex absorbing potential technique, we examined molecular systems with pyrene as the conductive wire and graphene or aza-graphene as electrodes. The calculated conductance values (6.20 × 10<sup>−4</sup> G₀ and 1.80 × 10<sup>−5</sup> G₀ for graphene and aza-graphene systems, respectively) reveal a tenfold increase in the graphene system due to transport through the LUMO orbital. The thermoelectric power values (0.5–2.5 μV·K<sup>−1</sup>) were comparable to those of gold-based systems. Chemical modifications, such as the insertion of NO₂ into pyrene, further enhanced conductance. These findings underline the molecular structure's critical role in determining transport properties and place graphene-based systems as viable thermoelectric materials.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115141"},"PeriodicalIF":3.0,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427688","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}
Utilizing density functional theory (DFT), we carried out a comprehensive analysis of the novel CsXH3 (X: Sc and Y) perovskite hydride's structural, mechanical, electronic, magnetic, thermodynamic, optical, and hydrogen storage properties. Through cohesive energy and elastic moduli calculations, we found that the CsXH3 compounds demonstrated both mechanical and thermal stability. For Sc and Y, the lattice constants in the crystal structure of CsXH3 (X: Sc and Y) compounds are 3.376 Å and 3.525 Å, respectively. Currently, the overall observations of band structure and electronic density of states are used to evaluate the metallic character of these compounds. These substances appear to be malleable materials, according to the B/G ratio (Pugh's ratio) study. Subsequent analysis indicated that the majority of their bond types are ionic. These compound features have led to the conclusion that they are non-magnetic order conductors. Furthermore, these materials have optical properties such as refractive index, dielectric function, absorption, and conductivity that show promise. According to our predictions, CsScH3 is a better hydride with exact optical characteristics. Vibrational stability of these crystalline materials was studied using molecular dynamics simulations and phonon dispersion curves. In addition, the study evaluated the CsXH3 compounds' ability to store hydrogen, resulting in 1.67 wt% for CsScH3 and 1.35 wt% for CsYH3. This discovery opens up new possibilities in the realm of hydrogen storage materials as it is the first analysis of CsXH3 perovskite hydrides.
{"title":"The first principles investigation of free‑lead perovskite-type hydrides CsXH3 (X = Sc, Y) for hydrogen storage application","authors":"M. Kashif Masood , Wahidullah Khan , Shumaila Bibi , Omer Munir , Shishir Timilsena , Javaria Kanwal , Javed Rehman , Razan A. Alshgari","doi":"10.1016/j.comptc.2025.115144","DOIUrl":"10.1016/j.comptc.2025.115144","url":null,"abstract":"<div><div>Utilizing density functional theory (DFT), we carried out a comprehensive analysis of the novel CsXH<sub>3</sub> (X: Sc and Y) perovskite hydride's structural, mechanical, electronic, magnetic, thermodynamic, optical, and hydrogen storage properties. Through cohesive energy and elastic moduli calculations, we found that the CsXH<sub>3</sub> compounds demonstrated both mechanical and thermal stability. For Sc and Y, the lattice constants in the crystal structure of CsXH<sub>3</sub> (X: Sc and Y) compounds are 3.376 Å and 3.525 Å, respectively. Currently, the overall observations of band structure and electronic density of states are used to evaluate the metallic character of these compounds. These substances appear to be malleable materials, according to the B/G ratio (Pugh's ratio) study. Subsequent analysis indicated that the majority of their bond types are ionic. These compound features have led to the conclusion that they are non-magnetic order conductors. Furthermore, these materials have optical properties such as refractive index, dielectric function, absorption, and conductivity that show promise. According to our predictions, CsScH<sub>3</sub> is a better hydride with exact optical characteristics. Vibrational stability of these crystalline materials was studied using molecular dynamics simulations and phonon dispersion curves. In addition, the study evaluated the CsXH<sub>3</sub> compounds' ability to store hydrogen, resulting in 1.67 wt% for CsScH<sub>3</sub> and 1.35 wt% for CsYH<sub>3</sub>. This discovery opens up new possibilities in the realm of hydrogen storage materials as it is the first analysis of CsXH<sub>3</sub> perovskite hydrides.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115144"},"PeriodicalIF":3.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143421825","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 : 2025-02-08DOI: 10.1016/j.comptc.2025.115125
Jingping Li , Huijie Guo , Yanan Zhong , Yuanzuo Li , Peng Song
To investigate the effects of varying π bridge lengths on the structural and electronic properties, two L-(D-π-A)2-type dye molecules were simulated using density functional theory (DFT). In this study, KS-19 employed thiophene as the π bridge, while KS-21 incorporated 2,2′-bithiophene. The optimized geometry revealed that the presence of 2,2′-bithiophene in the KS-21 molecule enhances its degree of conjugation, thereby exhibiting superior molecular stability. The additional thiophene unit in KS-21 was found to facilitate a red shift in the absorption spectra based on optical property analysis. Furthermore, 2,2′-bithiophene within the KS-21 molecule proved more effective for achieving dye regeneration and complete electron injection. Additionally, we simulated their adsorption behavior on titanium dioxide clusters and calculated their adsorption energies. Our investigation demonstrated that the KS-21 dye with a 2,2′-bithiophene π spacer exhibited enhanced photovoltaic performance. Consequently, double-anchored dyes incorporating extended π conjugated structures show significant promise across various applications in dye-sensitized solar cells.
{"title":"Theoretical study of novel xanthene-linked L-(D-π-a)2-type double-anchored dyes for dye-sensitized solar cells: Effects of π bridge length and TiO2 adsorption pattern","authors":"Jingping Li , Huijie Guo , Yanan Zhong , Yuanzuo Li , Peng Song","doi":"10.1016/j.comptc.2025.115125","DOIUrl":"10.1016/j.comptc.2025.115125","url":null,"abstract":"<div><div>To investigate the effects of varying π bridge lengths on the structural and electronic properties, two <sub>L</sub>-(D-π-A)<sub>2</sub>-type dye molecules were simulated using density functional theory (DFT). In this study, KS-19 employed thiophene as the π bridge, while KS-21 incorporated 2,2′-bithiophene. The optimized geometry revealed that the presence of 2,2′-bithiophene in the KS-21 molecule enhances its degree of conjugation, thereby exhibiting superior molecular stability. The additional thiophene unit in KS-21 was found to facilitate a red shift in the absorption spectra based on optical property analysis. Furthermore, 2,2′-bithiophene within the KS-21 molecule proved more effective for achieving dye regeneration and complete electron injection. Additionally, we simulated their adsorption behavior on titanium dioxide clusters and calculated their adsorption energies. Our investigation demonstrated that the KS-21 dye with a 2,2′-bithiophene π spacer exhibited enhanced photovoltaic performance. Consequently, double-anchored dyes incorporating extended π conjugated structures show significant promise across various applications in dye-sensitized solar cells.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115125"},"PeriodicalIF":3.0,"publicationDate":"2025-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143388035","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 : 2025-02-06DOI: 10.1016/j.comptc.2025.115127
Wanting Wang , Yuke Zuo , Ziqing Xi , He Yuan , Maoxia He , Ju Xie
Polycyclic aromatic hydrocarbons (PAHs) are a kind of carcinogenic substances, which exist widely in the environment. In order to effectively control PAHs, a molecular recognition strategy was reported by using X-diimide-pillar[4,6]arenes (X = Aryl group) as host compounds. X-diimide-pillar[4,6]arenes have stable topological structures with electron-deficient molecular cavities. Therefore, they were able to form host-guest inclusion complexes with PAH pollutants. For all inclusion complexes, the geometrical structures, electronic structures, non-covalent interactions, and thermodynamic stabilities were discussed systematically based on density functional theory (DFT) calculations. X-diimide-pillar[6]arenes had better recognition ability toward PAHs due to their larger molecular cavities. C-H···π and π···π stacking interactions were the main contributions to the formation of the host-guest complexes. Furthermore, molecular dynamics (MD) simulations showed that X-diimide-pillar[6]arenes could capture PAH molecules in solvents and exist stably in the form of host-guest complexes.
{"title":"Efficient molecular recognition of polycyclic aromatic hydrocarbons by X-diimide-pillar[4,6]arenes","authors":"Wanting Wang , Yuke Zuo , Ziqing Xi , He Yuan , Maoxia He , Ju Xie","doi":"10.1016/j.comptc.2025.115127","DOIUrl":"10.1016/j.comptc.2025.115127","url":null,"abstract":"<div><div>Polycyclic aromatic hydrocarbons (PAHs) are a kind of carcinogenic substances, which exist widely in the environment. In order to effectively control PAHs, a molecular recognition strategy was reported by using X-diimide-pillar[4,6]arenes (X = Aryl group) as host compounds. X-diimide-pillar[4,6]arenes have stable topological structures with electron-deficient molecular cavities. Therefore, they were able to form host-guest inclusion complexes with PAH pollutants. For all inclusion complexes, the geometrical structures, electronic structures, non-covalent interactions, and thermodynamic stabilities were discussed systematically based on density functional theory (DFT) calculations. X-diimide-pillar[6]arenes had better recognition ability toward PAHs due to their larger molecular cavities. C-H···π and π···π stacking interactions were the main contributions to the formation of the host-guest complexes. Furthermore, molecular dynamics (MD) simulations showed that X-diimide-pillar[6]arenes could capture PAH molecules in solvents and exist stably in the form of host-guest complexes.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115127"},"PeriodicalIF":3.0,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143328314","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 : 2025-02-04DOI: 10.1016/j.comptc.2025.115128
Sammed Patil, Praveenkumar Sappidi
Polybenzimidazoles (PBIs) are Ionenes with the charged benzimidazole present in the polymeric backbone. PBIs are classified as cationic or anionic ionones based on their charge, and they exhibit outstanding thermomechanical properties. PBIs have been extensively employed as membranes for a range of complex gas and liquid separations, and so on. In this paper, we employ all-atom molecular dynamics simulations to explore the behavior of two different forms of polybenzimidazole polymers in salt-water mixtures. The two polymers, namely polybenzimidazolides (PBI) (anionic form) and polybenzimidazoliums (PBIm) (cationic form), were considered in two different water-mixed salts such as (a) Sodium chloride (NaCl) and (b) Calcium chloride (CaCl2). We report on the intramolecular and intermolecular structural and dynamic properties of PBI and PBIm in saltwater. Our findings indicate that the radius of gyration (Rg) of both PBI and PBIm decreases as the concentrations of NaCl and CaCl2 increase. Analysis of the dihedral angle distribution reveals that the gauche conformation predominates for both polymers in the water-salt mixtures. The radial distribution function analysis between the nitrogen and carbon atoms of the imidazole group on PBI and PBIm and the salt ions shows notable structural peaks. In contrast, PBI and PBIm exhibit relatively weak interactions with water molecules. The hydrogen bonding interactions between PBI and water are particularly significant and contribute to various structural changes observed. In summary, this paper offers a comprehensive atomic-level description of the structural transitions responsible for the conformational behaviors of both PBI and PBIm.
{"title":"Structure and dynamic properties of Polybenzimidazolium and Polybenzimidazolide in a mixture of salt and water using all atom molecular dynamics simulations","authors":"Sammed Patil, Praveenkumar Sappidi","doi":"10.1016/j.comptc.2025.115128","DOIUrl":"10.1016/j.comptc.2025.115128","url":null,"abstract":"<div><div>Polybenzimidazoles (PBIs) are Ionenes with the charged benzimidazole present in the polymeric backbone. PBIs are classified as cationic or anionic ionones based on their charge, and they exhibit outstanding thermomechanical properties. PBIs have been extensively employed as membranes for a range of complex gas and liquid separations, and so on. In this paper, we employ all-atom molecular dynamics simulations to explore the behavior of two different forms of polybenzimidazole polymers in salt-water mixtures. The two polymers, namely polybenzimidazolides (PBI) (anionic form) and polybenzimidazoliums (PBIm) (cationic form), were considered in two different water-mixed salts such as (a) Sodium chloride (NaCl) and (b) Calcium chloride (CaCl<sub>2</sub>). We report on the intramolecular and intermolecular structural and dynamic properties of PBI and PBIm in saltwater. Our findings indicate that the radius of gyration (R<sub>g</sub>) of both PBI and PBIm decreases as the concentrations of NaCl and CaCl<sub>2</sub> increase. Analysis of the dihedral angle distribution reveals that the gauche conformation predominates for both polymers in the water-salt mixtures. The radial distribution function analysis between the nitrogen and carbon atoms of the imidazole group on PBI and PBIm and the salt ions shows notable structural peaks. In contrast, PBI and PBIm exhibit relatively weak interactions with water molecules. The hydrogen bonding interactions between PBI and water are particularly significant and contribute to various structural changes observed. In summary, this paper offers a comprehensive atomic-level description of the structural transitions responsible for the conformational behaviors of both PBI and PBIm.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115128"},"PeriodicalIF":3.0,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143388034","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 : 2025-02-03DOI: 10.1016/j.comptc.2025.115126
Yong Lai
CO2 emissions and their contribution to global climate change become a critical issue. Geological storage of CO2 in subterranean reservoirs, particularly in carbonate rocks, is one of the promising methods proposed to mitigate atmospheric CO2 levels. The research specifically explores the molecular-level interactions of CO2 with calcite, anorthite, and albite, which are key components of carbonate rock formations. Using a combination of Grand Canonical Monte Carlo (GCMC), molecular dynamics simulations (MDs), and density functional theory (DFT) methods, the study investigates CO2 adsorption behaviors within the slit nanopores of these minerals under varying conditions. The findings demonstrate that anorthite exhibits the highest CO2 adsorption capacity at lower pressures, although this advantage diminishes as pressure increases, leading to a more uniform adsorption capacity across the three minerals. The study also reveals that the presence of water significantly impairs CO2 adsorption, with higher water content further reducing adsorption efficiency.
{"title":"Molecular simulation of CO2 adsorption behavior by different stratigraphic conditions in geological storage","authors":"Yong Lai","doi":"10.1016/j.comptc.2025.115126","DOIUrl":"10.1016/j.comptc.2025.115126","url":null,"abstract":"<div><div>CO<sub>2</sub> emissions and their contribution to global climate change become a critical issue. Geological storage of CO<sub>2</sub> in subterranean reservoirs, particularly in carbonate rocks, is one of the promising methods proposed to mitigate atmospheric CO<sub>2</sub> levels. The research specifically explores the molecular-level interactions of CO<sub>2</sub> with calcite, anorthite, and albite, which are key components of carbonate rock formations. Using a combination of Grand Canonical Monte Carlo (GCMC), molecular dynamics simulations (MDs), and density functional theory (DFT) methods, the study investigates CO<sub>2</sub> adsorption behaviors within the slit nanopores of these minerals under varying conditions. The findings demonstrate that anorthite exhibits the highest CO<sub>2</sub> adsorption capacity at lower pressures, although this advantage diminishes as pressure increases, leading to a more uniform adsorption capacity across the three minerals. The study also reveals that the presence of water significantly impairs CO<sub>2</sub> adsorption, with higher water content further reducing adsorption efficiency.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115126"},"PeriodicalIF":3.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143328312","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 : 2025-02-03DOI: 10.1016/j.comptc.2025.115102
Walid Taouali , Amel Azazi , Rym Hassani , Entesar H. EL-Araby , Kamel Alimi
In this study, we designed four new non-fullerene acceptors (ANF1-ANF4) for organic photovoltaic cells derived from a well-known reference compound, Y15. The terminal acceptor of Y15 was modified by removing the chlorine atoms and adding a cyano group at four different positions. To explore the impact of the cynao group substitutions, we investigated the optoelectronic properties of the derived molecules using density functional theory (DFT) and time density functional theory (TD-DFT). We assessed several characteristics of the created compounds, including charge mobilities, molecular planarity parameters, molecular electrostatic potential, frontier molecular orbitals, transition density matrix, interfragment charge transfer (IFCT), and non-covalent interactions (NCI). Compared to the primary molecule Y15, we discovered that all tailored molecules have more planar geometries, a smaller energy gap ranging from 1.55 to 1.60 eV, and better optical properties with a maximum of absorption ranging from 759 nm to 796 nm in the chloroform phase. Moreover, we found that, except ANF4, all the other proposed molecules exhibit higher conductivity due to their lower reorganizational energy values compared to the reference molecule Y15. In particular, the investigation results showed that, given its promising optoelectronic and photovoltaic properties, ANF1 would be a great candidate for usage in the creation of high-performance organic solar cells.
{"title":"Exploring the impact of cyano substitutions in non-fullerene acceptors for enhanced organic solar cell performance: A DFT and TD-DFT investigation","authors":"Walid Taouali , Amel Azazi , Rym Hassani , Entesar H. EL-Araby , Kamel Alimi","doi":"10.1016/j.comptc.2025.115102","DOIUrl":"10.1016/j.comptc.2025.115102","url":null,"abstract":"<div><div>In this study, we designed four new non-fullerene acceptors (ANF1-ANF4) for organic photovoltaic cells derived from a well-known reference compound, Y15. The terminal acceptor of Y15 was modified by removing the chlorine atoms and adding a cyano group at four different positions. To explore the impact of the cynao group substitutions, we investigated the optoelectronic properties of the derived molecules using density functional theory (DFT) and time density functional theory (TD-DFT). We assessed several characteristics of the created compounds, including charge mobilities, molecular planarity parameters, molecular electrostatic potential, frontier molecular orbitals, transition density matrix, interfragment charge transfer (IFCT), and non-covalent interactions (NCI). Compared to the primary molecule Y15, we discovered that all tailored molecules have more planar geometries, a smaller energy gap ranging from 1.55 to 1.60 eV, and better optical properties with a maximum of absorption ranging from 759 nm to 796 nm in the chloroform phase. Moreover, we found that, except ANF4, all the other proposed molecules exhibit higher conductivity due to their lower reorganizational energy values compared to the reference molecule Y15. In particular, the investigation results showed that, given its promising optoelectronic and photovoltaic properties, ANF1 would be a great candidate for usage in the creation of high-performance organic solar cells.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1246 ","pages":"Article 115102"},"PeriodicalIF":3.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143349352","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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