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}
Pub Date : 2025-02-01DOI: 10.1016/j.comptc.2024.115022
Bin Liu , Wen-Lu Wang , Yan-Ni Su , Ya-Ling Ye , Wei-Ming Sun
The interaction between a boron-based Zn@B38 superatom and five drugs, including cisplatin (DDP), 5-fluorouracil (FU), mercaptopurine (MP), hydroxyurea (HU) and nitrogen mustard (CM) have been investigated. The adsorption of these anticancer drugs onto Zn@B38 reduces the energy gap of this superatom. Except for DDP, these drugs exhibit strong covalent interaction with the vertex of Zn@B38 because the lone pair of N/O atom of FU, MP, HU, and CM can fill into the empty atomic orbital of the electron-deficient boron atom of Zn@B38 to form polar covalent bonds, resulting in the charge transfer from drugs to Zn@B38. Hence, the adsorption energies of drug@[Zn@B38] (drug = FU, MP, HU, and CM) are −37.67 to −57.21 kcal/mol, but can be significantly decreased to −8.63–5.48 kcal/mol upon protonation, suggesting that these drugs can be efficiently adsorbed by the Zn@B38 carrier in neutral aqueous solution but are easily released in the acidic tumor microenvironment.
{"title":"On the potential of Zn@B38 superatom as a drug delivery vehicle for several anticancer drugs: A DFT study","authors":"Bin Liu , Wen-Lu Wang , Yan-Ni Su , Ya-Ling Ye , Wei-Ming Sun","doi":"10.1016/j.comptc.2024.115022","DOIUrl":"10.1016/j.comptc.2024.115022","url":null,"abstract":"<div><div>The interaction between a boron-based Zn@B<sub>38</sub> superatom and five drugs, including cisplatin (DDP), 5-fluorouracil (FU), mercaptopurine (MP), hydroxyurea (HU) and nitrogen mustard (CM) have been investigated. The adsorption of these anticancer drugs onto Zn@B<sub>38</sub> reduces the energy gap of this superatom. Except for DDP, these drugs exhibit strong covalent interaction with the vertex of Zn@B<sub>38</sub> because the lone pair of N/O atom of FU, MP, HU, and CM can fill into the empty atomic orbital of the electron-deficient boron atom of Zn@B<sub>38</sub> to form polar covalent bonds, resulting in the charge transfer from drugs to Zn@B<sub>38</sub>. Hence, the adsorption energies of drug@[Zn@B<sub>38</sub>] (drug = FU, MP, HU, and CM) are −37.67 to −57.21 kcal/mol, but can be significantly decreased to −8.63–5.48 kcal/mol upon protonation, suggesting that these drugs can be efficiently adsorbed by the Zn@B<sub>38</sub> carrier in neutral aqueous solution but are easily released in the acidic tumor microenvironment.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115022"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160005","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 : 2025-02-01DOI: 10.1016/j.comptc.2025.115074
Linian Li
This study examines the sensing performance of transition metal doped C7N3 sensor structures for four toxic gases (H2S, SO2, NO2, and NO). A series of sensor configurations with single transition metal atoms doped with C7N3 (TM-C7N3) are constructed. The results of the stability analysis indicate that, with the exception of Ni-C7N3, all sensor configurations demonstrate excellent structural stability. Notably, Os-C7N3 exhibits a high adsorption strength for four toxic gases. Furthermore, the adsorption strength of TM-C7N3 towards NO consistently surpasses that of the other gases investigated. Ultimately, by comparing recovery times, the most effective gas sensor is identified. At 298 K, Pd-C7N3 is a suitable H2S gas sensor, and Fe-C7N3 and Co-C7N3 are suitable SO2 gas sensors. At 398 K and above temperatures, Fe- and Rh-C7N3 are promising H2S gas sensors, and Pt-C7N3 is a promising SO2 and NO2 gas sensor.
{"title":"Investigating the adsorption and sensing of H2S, SO2, NO, and NO2 on transition metal atom doped C7N3 using DFT","authors":"Linian Li","doi":"10.1016/j.comptc.2025.115074","DOIUrl":"10.1016/j.comptc.2025.115074","url":null,"abstract":"<div><div>This study examines the sensing performance of transition metal doped C<sub>7</sub>N<sub>3</sub> sensor structures for four toxic gases (H<sub>2</sub>S, SO<sub>2</sub>, NO<sub>2</sub>, and NO). A series of sensor configurations with single transition metal atoms doped with C<sub>7</sub>N<sub>3</sub> (TM-C<sub>7</sub>N<sub>3</sub>) are constructed. The results of the stability analysis indicate that, with the exception of Ni-C<sub>7</sub>N<sub>3</sub>, all sensor configurations demonstrate excellent structural stability. Notably, Os-C<sub>7</sub>N<sub>3</sub> exhibits a high adsorption strength for four toxic gases. Furthermore, the adsorption strength of TM-C<sub>7</sub>N<sub>3</sub> towards NO consistently surpasses that of the other gases investigated. Ultimately, by comparing recovery times, the most effective gas sensor is identified. At 298 K, Pd-C<sub>7</sub>N<sub>3</sub> is a suitable H<sub>2</sub>S gas sensor, and Fe-C<sub>7</sub>N<sub>3</sub> and Co-C<sub>7</sub>N<sub>3</sub> are suitable SO<sub>2</sub> gas sensors. At 398 K and above temperatures, Fe- and Rh-C<sub>7</sub>N<sub>3</sub> are promising H<sub>2</sub>S gas sensors, and Pt-C<sub>7</sub>N<sub>3</sub> is a promising SO<sub>2</sub> and NO<sub>2</sub> gas sensor.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115074"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160052","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 quest for organic molecules with tunable optoelectronic properties for specific purposes is still continuing and computational designing strategies gain momentum in recent years. In this context, BOAPY core moiety attracts our attention due to its excellent photophysical properties and structural flexibility. Therefore, here we made an attempt to further enhance the photophysical properties of BOAPY molecule by introducing electron donating tuner group such as –OCH3, –NH2, –NH(CH3) and –N(CH3)2 as well as electron withdrawing flanking groups such as –F, –CF3 and –CN, one on each side of the tuner group. Totally, we have designed 25 molecules and analyzed their optical and Non-Linear Optical (NLO) properties using Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) calculations. These calculations are done at M06-2X/6-31+G(d,p) level of theory. The wavelength dependent NLO properties of the designed molecules are also determined. Our studies reveal that the HOMO-LUMO energy gap (ΔE) decreases with an increase in the electron donating nature of the tuner group. The electron withdrawing flanking groups such as –CF3 and –CN are acting well in reducing the ΔE value. The simulated absorption spectra of the designed molecules show that the λmax increases with the electron donating power of the tuner group. Electron Localization Function (ELF) and Localized Orbital Locator (LOL) topological analyses are done to ascertain the presence of delocalization in the designed molecules. Transition Density Matrix (TDM) Analysis is also done to quantify the intramolecular charge transfer. The NLO calculations show that all the designed molecules show superior NLO characteristics, with enhanced <α>, βtotal and <γ> values, surpassing urea, which is a standard NLO material. The wavelength dependent NLO calculations of a selected molecule reveal that the dynamic NLO descriptors fluctuate with wavelength and they are reaching their highest values at 450 nm. In summary, this study laid the foundation for the designing principles to tune the BOAPY derivatives to get enhanced optoelectronic and NLO properties.
{"title":"Tuning the BOAPY derivatives for enhancing the NLO properties using flanking groups – A DFT & TD-DFT study","authors":"Serangolam Krishnasami Sridhar , Rajadurai Vijay Solomon","doi":"10.1016/j.comptc.2024.115062","DOIUrl":"10.1016/j.comptc.2024.115062","url":null,"abstract":"<div><div>The quest for organic molecules with tunable optoelectronic properties for specific purposes is still continuing and computational designing strategies gain momentum in recent years. In this context, BOAPY core moiety attracts our attention due to its excellent photophysical properties and structural flexibility. Therefore, here we made an attempt to further enhance the photophysical properties of BOAPY molecule by introducing electron donating tuner group such as –OCH<sub>3</sub>, –NH<sub>2</sub>, –NH(CH<sub>3</sub>) and –N(CH<sub>3</sub>)<sub>2</sub> as well as electron withdrawing flanking groups such as –F, –CF<sub>3</sub> and –CN, one on each side of the tuner group. Totally, we have designed 25 molecules and analyzed their optical and Non-Linear Optical (NLO) properties using Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) calculations. These calculations are done at M06-2X/6-31+G(d,p) level of theory. The wavelength dependent NLO properties of the designed molecules are also determined. Our studies reveal that the HOMO-LUMO energy gap (ΔE) decreases with an increase in the electron donating nature of the tuner group. The electron withdrawing flanking groups such as –CF<sub>3</sub> and –CN are acting well in reducing the ΔE value. The simulated absorption spectra of the designed molecules show that the λ<sub>max</sub> increases with the electron donating power of the tuner group. Electron Localization Function (ELF) and Localized Orbital Locator (LOL) topological analyses are done to ascertain the presence of delocalization in the designed molecules. Transition Density Matrix (TDM) Analysis is also done to quantify the intramolecular charge transfer. The NLO calculations show that all the designed molecules show superior NLO characteristics, with enhanced <α>, β<sub>total</sub> and <γ> values, surpassing urea, which is a standard NLO material. The wavelength dependent NLO calculations of a selected molecule reveal that the dynamic NLO descriptors fluctuate with wavelength and they are reaching their highest values at 450 nm. In summary, this study laid the foundation for the designing principles to tune the BOAPY derivatives to get enhanced optoelectronic and NLO properties.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115062"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160078","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 : 2025-02-01DOI: 10.1016/j.comptc.2024.115064
A. Subashini , P. Venkatesan , G.Thulasi Prasanna , R. Kumaravel , M.Judith Percino , Helen Stoeckli-Evans , K. Ramamurthi
A new benzylideneaniline derivative, N-(4-nitrobenzylidene)-4’-fluoroaniline (I), was synthesized by a condensation reaction between 4-nitrobenzaldehyde and 4-fluoroaniline. The crystal structure of I was analyzed and compared with two regioisomeric benzylideneaniline derivatives, viz.N-(3-nitrobenzylidene)-4’-fluoroaniline (II) and N-(4-nitrobenzylidene)-2’-fluoroaniline (III), reported in the literature. The crystal structures of I-III were subjected to evaluation of their interatomic interactions in the crystal using Hirshfeld surface (HS) analysis and Coulomb-London-Pauli-PIXEL (CLP-PIXEL)and DFT calculations. The investigation reveals that the crystal packing of I–III was stabilized by the weak C–H⋅⋅⋅O, C–H⋅⋅⋅F and C–H⋅⋅⋅π interactions. Intermolecular interaction energies for different molecular pairs in the crystal packing of I-III, as well as the total lattice energies were quantified. The total lattice energies of the three regioisomeric benzylideneanilines (I-III) are compared and the dipole moment (μ), the polarizability (αtot) and the first-order hyperpolarizability (βtot) of I-III were computed using the M06-2X/cc-pVTZ level of theory.
{"title":"Evaluation of weak noncovalent interactions in three regioisomeric benzylideneaniline derivatives: An integrated crystallographic and theoretical approach","authors":"A. Subashini , P. Venkatesan , G.Thulasi Prasanna , R. Kumaravel , M.Judith Percino , Helen Stoeckli-Evans , K. Ramamurthi","doi":"10.1016/j.comptc.2024.115064","DOIUrl":"10.1016/j.comptc.2024.115064","url":null,"abstract":"<div><div>A new benzylideneaniline derivative, <em>N</em>-(4-nitrobenzylidene)-4’-fluoroaniline (<strong>I</strong>), was synthesized by a condensation reaction between 4-nitrobenzaldehyde and 4-fluoroaniline. The crystal structure of <strong>I</strong> was analyzed and compared with two regioisomeric benzylideneaniline derivatives, <em>viz.N</em>-(3-nitrobenzylidene)-4’-fluoroaniline (<strong>II</strong>) and <em>N</em>-(4-nitrobenzylidene)-2’-fluoroaniline (<strong>III</strong>), reported in the literature. The crystal structures of <strong>I-III</strong> were subjected to evaluation of their interatomic interactions in the crystal using Hirshfeld surface (HS) analysis and Coulomb-London-Pauli-PIXEL (CLP-PIXEL)and DFT calculations. The investigation reveals that the crystal packing of <strong>I</strong>–<strong>III</strong> was stabilized by the weak C–H⋅⋅⋅O, C–H⋅⋅⋅F and C–H⋅⋅⋅π interactions. Intermolecular interaction energies for different molecular pairs in the crystal packing of <strong>I-III</strong>, as well as the total lattice energies were quantified. The total lattice energies of the three regioisomeric benzylideneanilines (<strong>I-III</strong>) are compared and the dipole moment (μ), the polarizability (α<sub>tot</sub>) and the first-order hyperpolarizability (β<sub>tot</sub>) of <strong>I-III</strong> were computed using the M06-2X/cc-pVTZ level of theory.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115064"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160083","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 : 2025-02-01DOI: 10.1016/j.comptc.2025.115090
Wei Song , Zhe Fu , Jiale Liu , Jinqiang Li , Chaozheng He
NH3, as a carbon-free energy carrier that can replace H2, is also an important raw material for fertilizer. Compared with Haber–Bosch process, electrocatalytic NH3 synthesis has the green advantage of using renewable resources under ambient conditions. Herein, the catalytic performance of 3d transition metal single atom anchored in MoS2 (TM@MoS2) as electrocatalyst for nitrogen reduction reaction (NRR) has been investigated by first-principles calculation. By evaluating the stability, activity and selectivity of the catalysts, V@MoS2 was found to be a potential catalyst. After simulating the entire NRR pathway, it was found that the limiting potential was only −0.311 V, indicating that V@MoS2 had high catalytic activity. Finally, the partial density of states, charge density difference and crystal orbital Hamilton population were calculated to reveal the reason for the high catalytic activity of V@MoS2. We hope that this work can provide new design concepts for the development of efficient MoS2-based electrocatalysts.
{"title":"First-principles study of transition metal atom doped MoS2 as single-atom electrocatalysts for nitrogen fixation","authors":"Wei Song , Zhe Fu , Jiale Liu , Jinqiang Li , Chaozheng He","doi":"10.1016/j.comptc.2025.115090","DOIUrl":"10.1016/j.comptc.2025.115090","url":null,"abstract":"<div><div>NH<sub>3</sub>, as a carbon-free energy carrier that can replace H<sub>2</sub>, is also an important raw material for fertilizer. Compared with Haber–Bosch process, electrocatalytic NH<sub>3</sub> synthesis has the green advantage of using renewable resources under ambient conditions. Herein, the catalytic performance of 3d transition metal single atom anchored in MoS<sub>2</sub> (TM@MoS<sub>2</sub>) as electrocatalyst for nitrogen reduction reaction (NRR) has been investigated by first-principles calculation. By evaluating the stability, activity and selectivity of the catalysts, V@MoS<sub>2</sub> was found to be a potential catalyst. After simulating the entire NRR pathway, it was found that the limiting potential was only −0.311 V, indicating that V@MoS<sub>2</sub> had high catalytic activity. Finally, the partial density of states, charge density difference and crystal orbital Hamilton population were calculated to reveal the reason for the high catalytic activity of V@MoS<sub>2</sub>. We hope that this work can provide new design concepts for the development of efficient MoS<sub>2</sub>-based electrocatalysts.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115090"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160088","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 : 2025-02-01DOI: 10.1016/j.comptc.2024.115051
Indah Miftakhul Janah , Reka Mustika Sari , Faris Hermawan , Aulia Sukma Hutama , Lala Adetia Marlina
This study explores the potential of transition metal-doped Si12C12 nanocages for detecting volatile amines released during fish spoilage, using density functional theory (ωB97XD). The analysis focuses on structural stability, electronic properties, adsorption mechanisms, thermodynamics, sensitivity, and selectivity. Results indicate that TM doping enhances the adsorption of amines, with most interactions being spontaneous and exothermic. The trimethylamine∙∙∙TiSi11C12 complex exhibits particularly favorable thermodynamic properties. Sensitivity tests reveal that Cr, Cu, and Zn-doped nanocages demonstrate high responsiveness to trimethylamine at room temperature, with significant electronic property shifts upon adsorption. These findings highlight the potential of TM-doped Si12C12 nanocages as effective, selective, and sensitive sensors for monitoring volatile amines, aiding food quality control and fish freshness assessment. The study provides a theoretical basis for designing Si12C12-based gas sensors, contributing to advancements in food safety technology.
{"title":"A DFT study of doped first-row transition metals on Si12C12 nanocages as promising nanosensors for detecting volatile amines of fish spoilage","authors":"Indah Miftakhul Janah , Reka Mustika Sari , Faris Hermawan , Aulia Sukma Hutama , Lala Adetia Marlina","doi":"10.1016/j.comptc.2024.115051","DOIUrl":"10.1016/j.comptc.2024.115051","url":null,"abstract":"<div><div>This study explores the potential of transition metal-doped Si<sub>12</sub>C<sub>12</sub> nanocages for detecting volatile amines released during fish spoilage, using density functional theory (ωB97XD). The analysis focuses on structural stability, electronic properties, adsorption mechanisms, thermodynamics, sensitivity, and selectivity. Results indicate that TM doping enhances the adsorption of amines, with most interactions being spontaneous and exothermic. The trimethylamine∙∙∙TiSi<sub>11</sub>C<sub>12</sub> complex exhibits particularly favorable thermodynamic properties. Sensitivity tests reveal that Cr, Cu, and Zn-doped nanocages demonstrate high responsiveness to trimethylamine at room temperature, with significant electronic property shifts upon adsorption. These findings highlight the potential of TM-doped Si<sub>12</sub>C<sub>12</sub> nanocages as effective, selective, and sensitive sensors for monitoring volatile amines, aiding food quality control and fish freshness assessment. The study provides a theoretical basis for designing Si<sub>12</sub>C<sub>12</sub>-based gas sensors, contributing to advancements in food safety technology.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1244 ","pages":"Article 115051"},"PeriodicalIF":3.0,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143160651","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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