Pub Date : 2025-10-24DOI: 10.1016/j.comptc.2025.115559
Yu Shen , Zihan Shi , Xiushuang Zhou , Xu Hu , Tianliang Yao , Yongmin Huang
To address the need for low-cost hydroxylamine nitrate (HAN) propellant decomposition catalysts, research was conducted to investigate the catalytic reaction mechanism of Ru-based catalysts. Quantum chemical calculation methods were employed to study the catalytic decomposition mechanism of HAN molecules on the Ru(101) surface. The research results show that HAN primarily adsorbs on the catalyst surface in the form of RuO bond. First, the NO bond in the NO3−group of HAN undergoes cleavage, generating NO2 and O. Subsequently, O reacts with NH3OH, abstracting two H atoms to form NH2O and H2O. After the decomposition of HAN is completed, NH2O and NO2 undergo independent catalytic decomposition. For NH2O, the process starts with the cleavage of the NO bond, ultimately forming N and H2O, while for NO2, the decomposition involves the detachment of O atoms, eventually transforming N and O.
{"title":"The catalytic decomposition mechanism of hydroxylamine nitrate on the Ru(101) surface","authors":"Yu Shen , Zihan Shi , Xiushuang Zhou , Xu Hu , Tianliang Yao , Yongmin Huang","doi":"10.1016/j.comptc.2025.115559","DOIUrl":"10.1016/j.comptc.2025.115559","url":null,"abstract":"<div><div>To address the need for low-cost hydroxylamine nitrate (HAN) propellant decomposition catalysts, research was conducted to investigate the catalytic reaction mechanism of Ru-based catalysts. Quantum chemical calculation methods were employed to study the catalytic decomposition mechanism of HAN molecules on the Ru(101) surface. The research results show that HAN primarily adsorbs on the catalyst surface in the form of Ru<img>O bond. First, the N<img>O bond in the NO<sub>3</sub><sup>−</sup>group of HAN undergoes cleavage, generating NO<sub>2</sub> and O. Subsequently, O reacts with NH<sub>3</sub>OH, abstracting two H atoms to form NH<sub>2</sub>O and H<sub>2</sub>O. After the decomposition of HAN is completed, NH<sub>2</sub>O and NO<sub>2</sub> undergo independent catalytic decomposition. For NH<sub>2</sub>O, the process starts with the cleavage of the N<img>O bond, ultimately forming N and H<sub>2</sub>O, while for NO<sub>2</sub>, the decomposition involves the detachment of O atoms, eventually transforming N and O.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115559"},"PeriodicalIF":3.0,"publicationDate":"2025-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414262","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}
Various properties of BaHfX3 (X = S, Se) chalcogenide perovskites like structural, optical, phonon spectra, thermodynamic parameters along with the thermoelectric as well as electrical properties of these materials have been investigated. The Tran-Blaha modified Becke-Johnson potential (TB-mBJ) has been implemented for enhancing the accuracy in bandgap determination, as it yields more precise results for solid-state systems. These are semiconducting in nature disclosed by the band structure analysis. The observed results show good consistency with the available data. The dynamic stability of orthorhombic phase of BaHfX3 (X = S and Se) compositions is verified through phonon calculation. The thermodynamic parameters at different temperature range 300 K to 800 K in which Dulong-Petit limit shows the phase stability and the elastic property calculations validate the mechanical robustness of these compounds. The Spectroscopic Limited Maximum Efficiency (SLME) study also illustrates that these materials are intriguing candidates for photovoltaic applications due to their performance, cost-effectiveness, and suitable bandgap.
{"title":"Emerging potential chalcogenide perovskites BaHfX3 (X = S, Se) for energy conversion devices: Photovoltaic applications","authors":"Naincy Pandit , Rashmi Singh , Manendra S. Chauhan , Tarun Kumar Joshi , Anusha Dubey , Kulwinder Kaur , Rajeev Gupta , Tanuj Kumar , Samah Al-Qaisi , Ajay Singh Verma","doi":"10.1016/j.comptc.2025.115556","DOIUrl":"10.1016/j.comptc.2025.115556","url":null,"abstract":"<div><div>Various properties of BaHfX<sub>3</sub> (X = S, Se) chalcogenide perovskites like structural, optical, phonon spectra, thermodynamic parameters along with the thermoelectric as well as electrical properties of these materials have been investigated. The Tran-Blaha modified Becke-Johnson potential (TB-mBJ) has been implemented for enhancing the accuracy in bandgap determination, as it yields more precise results for solid-state systems. These are semiconducting in nature disclosed by the band structure analysis. The observed results show good consistency with the available data. The dynamic stability of orthorhombic phase of BaHfX<sub>3</sub> (X = S and Se) compositions is verified through phonon calculation. The thermodynamic parameters at different temperature range 300 K to 800 K in which Dulong-Petit limit shows the phase stability and the elastic property calculations validate the mechanical robustness of these compounds. The Spectroscopic Limited Maximum Efficiency (SLME) study also illustrates that these materials are intriguing candidates for photovoltaic applications due to their performance, cost-effectiveness, and suitable bandgap.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115556"},"PeriodicalIF":3.0,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414222","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 : 2025-10-22DOI: 10.1016/j.comptc.2025.115553
Boxin Cheng , Xiuzhong Fang , Meijuan Cao , Xiang Wang , Xianglan Xu
DFT calculations were used to examine how the electronic structure of TiO2 supports affects CO2 methanation on Ru4 clusters. The electronic structure of nL-TiO2 varies with the number of layers, and the binding ability of its two-coordinated surface oxygen atoms with metals differs. The 3 L-TiO2 binds Ru4 more strongly and obtains more electrons than 2 L-TiO2, indicative of stronger metal-support interactions. Mechanistic analysis reveals that CO2 methanation proceeds via competing CO* and HCOO* pathways on Ru4/2 L-TiO2, whereas the reaction through the HCOO* pathway on Ru4/2 L-TiO2 requires a substantially lower energy barrier. The origin of the alteration of the optimal pathway and the lower barrier is attributed to the stronger metal–support interactions weakening CO2* adsorption on Ru4/3 L-TiO2 without comparable destabilization of the downstream intermediates compared to Ru4/2 L-TiO2. The results establish the electronic structure of oxide supports as a crucial factor for advanced CO2 methanation catalysts.
{"title":"Support's electronic structure tuning CO2 methanation on Ru4/TiO2 catalysts: A DFT study","authors":"Boxin Cheng , Xiuzhong Fang , Meijuan Cao , Xiang Wang , Xianglan Xu","doi":"10.1016/j.comptc.2025.115553","DOIUrl":"10.1016/j.comptc.2025.115553","url":null,"abstract":"<div><div>DFT calculations were used to examine how the electronic structure of TiO<sub>2</sub> supports affects CO<sub>2</sub> methanation on Ru<sub>4</sub> clusters. The electronic structure of nL-TiO<sub>2</sub> varies with the number of layers, and the binding ability of its two-coordinated surface oxygen atoms with metals differs. The 3 L-TiO<sub>2</sub> binds Ru<sub>4</sub> more strongly and obtains more electrons than 2 L-TiO<sub>2</sub>, indicative of stronger metal-support interactions. Mechanistic analysis reveals that CO<sub>2</sub> methanation proceeds via competing CO* and HCOO* pathways on Ru<sub>4</sub>/2 L-TiO<sub>2</sub>, whereas the reaction through the HCOO* pathway on Ru<sub>4</sub>/2 L-TiO<sub>2</sub> requires a substantially lower energy barrier. The origin of the alteration of the optimal pathway and the lower barrier is attributed to the stronger metal–support interactions weakening CO<sub>2</sub>* adsorption on Ru<sub>4</sub>/3 L-TiO<sub>2</sub> without comparable destabilization of the downstream intermediates compared to Ru<sub>4</sub>/2 L-TiO<sub>2</sub>. The results establish the electronic structure of oxide supports as a crucial factor for advanced CO<sub>2</sub> methanation catalysts.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115553"},"PeriodicalIF":3.0,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414221","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 : 2025-10-21DOI: 10.1016/j.comptc.2025.115555
Jibiao Xie , Anna S. Savchenkova , Alexander M. Mebel , Alexander A. Konnov
High-temperature decomposition of pyridine, C5H5N, occurs during waste incineration, pyrolysis of biomass and coal. In the present work, the rate constants of H atom abstraction from C5H5N by H, CH3, CN, C2H3, CHCHCN and nC4H3 radicals have been calculated at the DLPNO-CCSD(T)-F12/cc-pVDZ-F12//M06-2X/def2-TZVP level of theory from 300 to 2000 K. The new rate constants obtained in the present work, in most cases are notably different from the expressions suggested in the earlier studies on pyridine pyrolysis or derived in theoretical calculations. Only for reactions of H atom abstraction by H, a reasonable agreement was found. It was revealed that the formation of ortho-, meta-, and para-pyridyls could be of equal importance and, therefore, all pyridyl isomers should be considered in detailed kinetic mechanisms for pyridine.
{"title":"Revisiting the kinetics of pyridine pyrolysis. Part 1: H atom abstraction reactions","authors":"Jibiao Xie , Anna S. Savchenkova , Alexander M. Mebel , Alexander A. Konnov","doi":"10.1016/j.comptc.2025.115555","DOIUrl":"10.1016/j.comptc.2025.115555","url":null,"abstract":"<div><div>High-temperature decomposition of pyridine, C<sub>5</sub>H<sub>5</sub>N, occurs during waste incineration, pyrolysis of biomass and coal. In the present work, the rate constants of H atom abstraction from C<sub>5</sub>H<sub>5</sub>N by H, CH<sub>3</sub>, CN, C<sub>2</sub>H<sub>3</sub>, CHCHCN and nC<sub>4</sub>H<sub>3</sub> radicals have been calculated at the DLPNO-CCSD(T)-F12/cc-pVDZ-F12//M06-2X/def2-TZVP level of theory from 300 to 2000 K. The new rate constants obtained in the present work, in most cases are notably different from the expressions suggested in the earlier studies on pyridine pyrolysis or derived in theoretical calculations. Only for reactions of H atom abstraction by H, a reasonable agreement was found. It was revealed that the formation of ortho-, meta-, and para-pyridyls could be of equal importance and, therefore, all pyridyl isomers should be considered in detailed kinetic mechanisms for pyridine.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115555"},"PeriodicalIF":3.0,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414268","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 : 2025-10-21DOI: 10.1016/j.comptc.2025.115548
Nure Alam Chowdhury , Thuy Hoai Linh Vuong , Maydenee Maydur Tresa , Albert Jojo , Jacob Rajan Munjanattu , Leaford Nathan Adebayo Henderson , Olusola Pelumi Oyeku , Abu Kaisar Mohammad Masum , Jayan Thomas
Sulfide-based solid-state electrolytes (SBSSEs) offer a promising solution to mitigate overcharging, overheating, and mechanical degradation issues associated with organic liquid electrolytes in lithium-ion batteries (LIBs). The ionic conductivity (IC) of SBSSEs has been enhanced through the incorporation of various dopants. Our dataset comprises ten features, including seven experimental results and three elemental properties of the dopants. Pearson correlation coefficient reveals that the concentration of dopant and electronegativity can influence the IC of SBSSEs. We applied three different machine learning models for regression analysis. Among them, the XGBoost model demonstrated superior predictive performance, achieving a R2 value of 0.83 in forecasting the discharge capacity of SBSSE-based LIBs. It is also observed that “Current” and IC can play a major role in determining the performance of the SBSSEs. These findings provide valuable insights for designing optimized SBSSEs before experimental synthesis, helping researchers in the development of next-generation solid-state electrolytes.
{"title":"Data-driven prediction of discharge capacity of Li-ion batteries in the presence of solid electrolyte","authors":"Nure Alam Chowdhury , Thuy Hoai Linh Vuong , Maydenee Maydur Tresa , Albert Jojo , Jacob Rajan Munjanattu , Leaford Nathan Adebayo Henderson , Olusola Pelumi Oyeku , Abu Kaisar Mohammad Masum , Jayan Thomas","doi":"10.1016/j.comptc.2025.115548","DOIUrl":"10.1016/j.comptc.2025.115548","url":null,"abstract":"<div><div>Sulfide-based solid-state electrolytes (SBSSEs) offer a promising solution to mitigate overcharging, overheating, and mechanical degradation issues associated with organic liquid electrolytes in lithium-ion batteries (LIBs). The ionic conductivity (IC) of SBSSEs has been enhanced through the incorporation of various dopants. Our dataset comprises ten features, including seven experimental results and three elemental properties of the dopants. Pearson correlation coefficient reveals that the concentration of dopant and electronegativity can influence the IC of SBSSEs. We applied three different machine learning models for regression analysis. Among them, the XGBoost model demonstrated superior predictive performance, achieving a R<sup>2</sup> value of 0.83 in forecasting the discharge capacity of SBSSE-based LIBs. It is also observed that “Current” and IC can play a major role in determining the performance of the SBSSEs. These findings provide valuable insights for designing optimized SBSSEs before experimental synthesis, helping researchers in the development of next-generation solid-state electrolytes.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115548"},"PeriodicalIF":3.0,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145358442","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 : 2025-10-21DOI: 10.1016/j.comptc.2025.115547
Junzhuo Xu , Hongyan Liu , Furong Sun , Hairong Zhang , Lixia Ling , Riguang Zhang , Maohong Fan , Baojun Wang , Chun Jin , Lin Xu
This work studies the reaction mechanism of the formation of xylenes from trimethylcyclopentane on the [GaH]2+ active site of Ga-ZSM-5 using the ONIOM (ob97xd/6-31G(d,p):pm6) method. The results show that the rate-determning step in the process from trimethylcyclopentane to xylene to produce o-xylene, m-xylene and p-xylene is entirely the ring expansion process. m-xylene is the easiest to produce, followed by p-xylene, and finally o-xylene. This result indicates that a large amount of xylene obtained in the experiment comes from the methylation of toluene, rather than directly generated from trimethylcyclopentane. Our discovery provides a new understanding of the formation of xylene during MTA on Ga-ZSM-5 catalysts.
{"title":"Revealing the mechanism of xylene from trimethylcyclopentane in MTA catalyzed by Ga-ZSM-5","authors":"Junzhuo Xu , Hongyan Liu , Furong Sun , Hairong Zhang , Lixia Ling , Riguang Zhang , Maohong Fan , Baojun Wang , Chun Jin , Lin Xu","doi":"10.1016/j.comptc.2025.115547","DOIUrl":"10.1016/j.comptc.2025.115547","url":null,"abstract":"<div><div>This work studies the reaction mechanism of the formation of xylenes from trimethylcyclopentane on the [GaH]<sup>2+</sup> active site of Ga-ZSM-5 using the ONIOM (ob97xd/6-31G(d,p):pm6) method. The results show that the rate-determning step in the process from trimethylcyclopentane to xylene to produce o-xylene, m-xylene and p-xylene is entirely the ring expansion process. m-xylene is the easiest to produce, followed by p-xylene, and finally o-xylene. This result indicates that a large amount of xylene obtained in the experiment comes from the methylation of toluene, rather than directly generated from trimethylcyclopentane. Our discovery provides a new understanding of the formation of xylene during MTA on Ga-ZSM-5 catalysts.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115547"},"PeriodicalIF":3.0,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340417","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 : 2025-10-21DOI: 10.1016/j.comptc.2025.115544
Bahadır Salmankurt
This study presents a theoretical investigation of Carbamazepine, Metformin, Paracetamol interacting with pristine and Au-decorated Molybdenum Disulfide (MoS2) using Density Functional Theory for the first time. Optimized geometries, interaction energies, electronic band structures, partial density of states, molecular dynamics (MD), and quantum transport results were analyzed. The calculated interaction energies were found to be strong compared to literature values, indicating that these molecules can be effectively removed from the environment, particularly with MoS2+Au. MD simulations show that the systems are stable at 300 K. Electronic band calculations reveal that the band gap of MoS2 is modified upon molecular adsorption, especially for Carbamazepine and Metformin, which is promising for sensing applications. Finally, quantum transport calculations were conducted to evaluate the sensitivity and selectivity of the molecules via the monolayers. The results indicate that Metformin and Paracetamol can be distinguished based on their electronic responses.
{"title":"Ab-Initio study of the interaction of pristine and Au-decorated Molybdenum Disulfide monolayer with the emerging contaminant pharmaceuticals","authors":"Bahadır Salmankurt","doi":"10.1016/j.comptc.2025.115544","DOIUrl":"10.1016/j.comptc.2025.115544","url":null,"abstract":"<div><div>This study presents a theoretical investigation of Carbamazepine, Metformin, Paracetamol interacting with pristine and Au-decorated Molybdenum Disulfide (MoS<sub>2</sub>) using Density Functional Theory for the first time. Optimized geometries, interaction energies, electronic band structures, partial density of states, molecular dynamics (MD), and quantum transport results were analyzed. The calculated interaction energies were found to be strong compared to literature values, indicating that these molecules can be effectively removed from the environment, particularly with MoS<sub>2</sub>+Au. MD simulations show that the systems are stable at 300 K. Electronic band calculations reveal that the band gap of MoS<sub>2</sub> is modified upon molecular adsorption, especially for Carbamazepine and Metformin, which is promising for sensing applications. Finally, quantum transport calculations were conducted to evaluate the sensitivity and selectivity of the molecules via the monolayers. The results indicate that Metformin and Paracetamol can be distinguished based on their electronic responses.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115544"},"PeriodicalIF":3.0,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145358352","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 : 2025-10-19DOI: 10.1016/j.comptc.2025.115550
Junyong Wu
Four types of complexes formed between furan (C4H4O) and CuX (X = F, Cl, Br, and I) and stabilized by hydrogen bonds, coexisting lone pair-π/π-halogen bonds, σ‑copper bonds and π‑copper bonds respectively have been systematically explored at the MP2/aug-cc-pVTZ-PP level to compare the relative strength and the interaction mechanism of each bond type. A comparison of the calculated binding energies reveals that σ‑copper bonds and π‑copper bonds are significantly stronger than hydrogen bonds and coexisting lone pair-π/π-halogen bonds, and within the regium bonds category, π‑copper bonds are stronger than their corresponding σ‑copper bonds. For hydrogen bonds, the attractive forces are dominated jointly by electrostatic and dispersion interactions; For complexes with coexisting lone pair-π/π-halogen bonds, dispersion interactions serve as the primary driving force. In contrast, the inherent stability of σ‑copper bond complexes and π‑copper bond complexes stems primarily from electrostatic energies and induction energies.
{"title":"Theoretical study on the nature of hydrogen bonds, coexisting lone pair-π/π-halogen bonds, σ‑copper bonds, and π‑copper bonds in furan-CuX complexes","authors":"Junyong Wu","doi":"10.1016/j.comptc.2025.115550","DOIUrl":"10.1016/j.comptc.2025.115550","url":null,"abstract":"<div><div>Four types of complexes formed between furan (C<sub>4</sub>H<sub>4</sub>O) and CuX (X = F, Cl, Br, and I) and stabilized by hydrogen bonds, coexisting lone pair-π/π-halogen bonds, σ‑copper bonds and π‑copper bonds respectively have been systematically explored at the MP2/aug-cc-pVTZ-PP level to compare the relative strength and the interaction mechanism of each bond type. A comparison of the calculated binding energies reveals that σ‑copper bonds and π‑copper bonds are significantly stronger than hydrogen bonds and coexisting lone pair-π/π-halogen bonds, and within the regium bonds category, π‑copper bonds are stronger than their corresponding σ‑copper bonds. For hydrogen bonds, the attractive forces are dominated jointly by electrostatic and dispersion interactions; For complexes with coexisting lone pair-π/π-halogen bonds, dispersion interactions serve as the primary driving force. In contrast, the inherent stability of σ‑copper bond complexes and π‑copper bond complexes stems primarily from electrostatic energies and induction energies.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115550"},"PeriodicalIF":3.0,"publicationDate":"2025-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145358443","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}
First-principles DFT calculations show that SrWN₃ adopts a distorted triclinic (P1) perovskite structure with pronounced octahedral tilts (tolerance factor t ≈ 1.00). The material is a semiconductor with a direct band gap of ∼1.0 eV, arising from strong W 5d – N 2p orbital hybridisation. Thermoelectric transport calculations predict a high-power factor ∼ 1 × 1011 W/m·K2), electrical conductivity ∼1 × 1019 S/m at 300 K, and ZT = ∼1, indicating efficient waste-heat conversion potential. Optically, SrWN₃ exhibits a high static dielectric constant ∼9 and strong absorption 6 × 105 cm−1 across the visible–UV range, with a plasmon resonance near 50 eV, suggesting suitability for light-harvesting and UV-shielding applications. Phonon spectra show no imaginary modes, and the Debye temperature is ∼850 K, with heat capacity saturating ∼58 J/mol·K at high T, signifying exceptional thermal stability. Together, these quantitative results highlight SrWN₃ as a multifunctional nitride perovskite with promising electronic, thermoelectric, optical and thermal properties for next-generation energy and high-temperature technologies.
{"title":"Unveiling the Multifunctional Properties of SrWN₃ Nitride Perovskite: A DFT Study on Structural, Electronic, Optical, Thermoelectric, and Thermodynamic Properties for Next-Generation Energy Applications","authors":"Nisha Mahepal, Trilok Akhani, Mitesh Solanki, Bhavik Thacker","doi":"10.1016/j.comptc.2025.115552","DOIUrl":"10.1016/j.comptc.2025.115552","url":null,"abstract":"<div><div>First-principles DFT calculations show that SrWN₃ adopts a distorted triclinic (P1) perovskite structure with pronounced octahedral tilts (tolerance factor t ≈ 1.00). The material is a semiconductor with a direct band gap of ∼1.0 eV, arising from strong W 5d – N 2p orbital hybridisation. Thermoelectric transport calculations predict a high-power factor ∼ 1 × 10<sup>11</sup> W/m·K<sup>2</sup>), electrical conductivity ∼1 × 10<sup>19</sup> S/m at 300 K, and ZT = ∼1, indicating efficient waste-heat conversion potential. Optically, SrWN₃ exhibits a high static dielectric constant ∼9 and strong absorption 6 × 10<sup>5</sup> cm<sup>−1</sup> across the visible–UV range, with a plasmon resonance near 50 eV, suggesting suitability for light-harvesting and UV-shielding applications. Phonon spectra show no imaginary modes, and the Debye temperature is ∼850 K, with heat capacity saturating ∼58 J/mol·K at high T, signifying exceptional thermal stability. Together, these quantitative results highlight SrWN₃ as a multifunctional nitride perovskite with promising electronic, thermoelectric, optical and thermal properties for next-generation energy and high-temperature technologies.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115552"},"PeriodicalIF":3.0,"publicationDate":"2025-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145474622","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 : 2025-10-17DOI: 10.1016/j.comptc.2025.115549
Sanjib Deuri
The nature of the BC triple bond has been investigated in diverse electronic environments using density functional theory at the M06-2X/aug-cc-pVTZ level. The feasibility of stabilizing triply bonded RC ≡ BR′ species was evaluated across a series of 19 model systems incorporating hydrogen and a range of small substituents (BH2, CH3, NH3, OH, F, CN). Bonding characteristics and their variation within the series were analyzed through topological examination of the Electron Localization Function (ELF), Atoms-in-Molecules (AIM) theory-based indices, and Natural Bond Orbital (NBO) analysis. The results indicate that CH3 substitution at the carbon end and NH2 substitution at both termini can effectively stabilize a genuine BC triple bond. Across all species, the BC linkage is found to be predominantly carbon-centered and polar in nature.
{"title":"Exploring the nature of boron carbon triple bond through substituent effects: ELF, AIM and NBO study","authors":"Sanjib Deuri","doi":"10.1016/j.comptc.2025.115549","DOIUrl":"10.1016/j.comptc.2025.115549","url":null,"abstract":"<div><div>The nature of the B<img>C triple bond has been investigated in diverse electronic environments using density functional theory at the M06-2X/aug-cc-pVTZ level. The feasibility of stabilizing triply bonded RC ≡ BR′ species was evaluated across a series of 19 model systems incorporating hydrogen and a range of small substituents (BH<sub>2</sub>, CH<sub>3</sub>, NH<sub>3</sub>, OH, F, CN). Bonding characteristics and their variation within the series were analyzed through topological examination of the Electron Localization Function (ELF), Atoms-in-Molecules (AIM) theory-based indices, and Natural Bond Orbital (NBO) analysis. The results indicate that CH<sub>3</sub> substitution at the carbon end and NH<sub>2</sub> substitution at both termini can effectively stabilize a genuine B<img>C triple bond. Across all species, the BC linkage is found to be predominantly carbon-centered and polar in nature.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1254 ","pages":"Article 115549"},"PeriodicalIF":3.0,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145358437","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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