Pub Date : 2025-04-17DOI: 10.1016/j.comptc.2025.115243
Shizhuo Wang , Yifan Ma , Xuechao Feng , Yang Yang , Luogang Xie , Shiquan Feng
Due to the retention of the strong redox active sites, 2D Z-scheme heterostructures exhibit many advantages in photocatalytic water splitting for hydrogen production. In this paper, based on Janus-WSSe and HfZrCO2 monolayers, we designed 24 van der Waals (vdW) WSe2/HfZrCO2 heterostructures, and selected out one Z-scheme heterostructure (HS) that most likely to serve as a water splitting photocatalyst for further study. Then, through first principles calculations, the stability, electronic and optical properties and photocatalytic water splitting mechanism for the HS were studied in detail. The results show that it is a promising Z-scheme water splitting photocatalyst in both neutral and acidic environments.
由于保留了强氧化还原活性位点，二维 Z 型异质结构在光催化水分离制氢方面表现出许多优势。本文以 Janus-WSSe 和 HfZrCO2 单层为基础，设计了 24 种范德华（vdW）WSe2/HfZrCO2 异质结构，并筛选出一种最有可能用作光催化水分离的 Z 型异质结构（HS）进行进一步研究。然后，通过第一性原理计算，详细研究了该异质结构的稳定性、电子和光学性质以及光催化分水机理。研究结果表明，无论在中性还是酸性环境中，它都是一种很有前途的 Z 型光催化剂。
{"title":"Study of direct Z-scheme water splitting photocatalytic Janus-WSSe/HfZrCO2 vdW heterostructures: First principles calculations","authors":"Shizhuo Wang , Yifan Ma , Xuechao Feng , Yang Yang , Luogang Xie , Shiquan Feng","doi":"10.1016/j.comptc.2025.115243","DOIUrl":"10.1016/j.comptc.2025.115243","url":null,"abstract":"<div><div>Due to the retention of the strong redox active sites, 2D <em>Z</em>-scheme heterostructures exhibit many advantages in photocatalytic water splitting for hydrogen production. In this paper, based on Janus-WSSe and HfZrCO<sub>2</sub> monolayers, we designed 24 van der Waals (vdW) WSe<sub>2</sub>/HfZrCO<sub>2</sub> heterostructures, and selected out one <em>Z</em>-scheme heterostructure (HS) that most likely to serve as a water splitting photocatalyst for further study. Then, through first principles calculations, the stability, electronic and optical properties and photocatalytic water splitting mechanism for the HS were studied in detail. The results show that it is a promising <em>Z</em>-scheme water splitting photocatalyst in both neutral and acidic environments.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115243"},"PeriodicalIF":3.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143852059","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 : 2025-04-15DOI: 10.1016/j.comptc.2025.115239
Md Rabbi Talukder , Md. Mehedi Hasan , Nadim Mahmood Nayeem , Md. Rafiqul Islam , Jehan Y. Al-Humaidi , Md Rasidul Islam , Md Masud Rana
Non-toxic halide cubic perovskites set the standard for the commercialization of optoelectronic and photovoltaic devices. Because of their enormous importance, a comprehensive analysis of the physical characteristics of cubic Ba3MX3 (M = P, Sb; X = F, Cl) perovskites was analyzed in this study utilizing ab initio Density Functional Theory. The thermodynamic stability of the explored materials was validated by negative formation energies, while the simulated XRD spectra firmly solidified that all the perovskites exhibit cubic structures. The GGA-PBE functional unveiled direct band gaps of 0.95 eV, 0.96 eV, 1.07 eV, and 0.99 eV for the semiconducting perovskites Ba3PF3, Ba3PCl3, Ba3SbF3, and Ba3SbCl3, respectively. The HSE06 potential unveiled refined band gaps of 1.42 eV, 1.50 eV, 1.96 eV, and 1.89 eV for the respective perovskites, emphasizing their potential as viable options for solar cell technologies. Moreover, the explored materials exhibited excellent absorption, high photoconductivity, an ideal refractive index, lower reflectivity, and minimal loss function in the visible spectrum, rendering them outstanding contenders for solar cell applications. The Born stability benchmarks validated the mechanical stability of all the explored perovskites. Additionally, their inherent stiffness, hardness, toughness, brittleness, and anisotropic behavior are vital for long-term durability in engineering applications. Thermodynamic assessments validated the thermal stability of these perovskites at wide temperature ranges. The study's findings revealed that Ba3MX3 (M = P, Sb; X = F, Cl) perovskites could emerge as promising optical materials, and their synthesis in the upcoming days is highly anticipated.
{"title":"Theoretical insights into novel Ba3MX3 (M = P, Sb; X = F, Cl) perovskites for advanced optoelectronics: A first-principles DFT study","authors":"Md Rabbi Talukder , Md. Mehedi Hasan , Nadim Mahmood Nayeem , Md. Rafiqul Islam , Jehan Y. Al-Humaidi , Md Rasidul Islam , Md Masud Rana","doi":"10.1016/j.comptc.2025.115239","DOIUrl":"10.1016/j.comptc.2025.115239","url":null,"abstract":"<div><div>Non-toxic halide cubic perovskites set the standard for the commercialization of optoelectronic and photovoltaic devices. Because of their enormous importance, a comprehensive analysis of the physical characteristics of cubic Ba<sub>3</sub>MX<sub>3</sub> (M = P, Sb; X = F, Cl) perovskites was analyzed in this study utilizing ab initio Density Functional Theory. The thermodynamic stability of the explored materials was validated by negative formation energies, while the simulated XRD spectra firmly solidified that all the perovskites exhibit cubic structures. The GGA-PBE functional unveiled direct band gaps of 0.95 eV, 0.96 eV, 1.07 eV, and 0.99 eV for the semiconducting perovskites Ba<sub>3</sub>PF<sub>3</sub>, Ba<sub>3</sub>PCl<sub>3</sub>, Ba<sub>3</sub>SbF<sub>3</sub>, and Ba<sub>3</sub>SbCl<sub>3</sub>, respectively. The HSE06 potential unveiled refined band gaps of 1.42 eV, 1.50 eV, 1.96 eV, and 1.89 eV for the respective perovskites, emphasizing their potential as viable options for solar cell technologies. Moreover, the explored materials exhibited excellent absorption, high photoconductivity, an ideal refractive index, lower reflectivity, and minimal loss function in the visible spectrum, rendering them outstanding contenders for solar cell applications. The Born stability benchmarks validated the mechanical stability of all the explored perovskites. Additionally, their inherent stiffness, hardness, toughness, brittleness, and anisotropic behavior are vital for long-term durability in engineering applications. Thermodynamic assessments validated the thermal stability of these perovskites at wide temperature ranges. The study's findings revealed that Ba<sub>3</sub>MX<sub>3</sub> (M = P, Sb; X = F, Cl) perovskites could emerge as promising optical materials, and their synthesis in the upcoming days is highly anticipated.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115239"},"PeriodicalIF":3.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835241","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 : 2025-04-15DOI: 10.1016/j.comptc.2025.115240
Ge Feng
The advancement of novel ceramic composite materials is advantageous for improving the design quality and performance of ceramic devices. This study utilizes first-principles computational methods to develop SiC/WS2 heterojunction composite materials, specifically SiC/WS2, SiC/WS2/SiC, and WS2/SiC/WS2, and examines the modulation of their properties through the application of biaxial and vertical strain. The findings reveal that all three types of SiC/WS2 heterojunctions exhibit commendable structural stability. Furthermore, each heterojunction displays direct bandgap semiconductor characteristics, with bandgap energies ranging from 1.392 eV to 1.479 eV. The application of strain systematically influences the electronic properties of the SiC/WS2 heterojunctions, with the three-layer heterojunction demonstrating heightened sensitivity to strain effects. This three-layer configuration also exhibits enhanced interlayer charge transfer and light absorption capabilities. The superior electronic properties of the SiC/WS2 heterojunctions underscore their potential utility in electronic and optoelectronic ceramic devices.
{"title":"Theoretical study of SiC/WS2 layered heterojunction composite ceramics: Promoting ceramic process design","authors":"Ge Feng","doi":"10.1016/j.comptc.2025.115240","DOIUrl":"10.1016/j.comptc.2025.115240","url":null,"abstract":"<div><div>The advancement of novel ceramic composite materials is advantageous for improving the design quality and performance of ceramic devices. This study utilizes first-principles computational methods to develop SiC/WS<sub>2</sub> heterojunction composite materials, specifically SiC/WS<sub>2</sub>, SiC/WS<sub>2</sub>/SiC, and WS<sub>2</sub>/SiC/WS<sub>2</sub>, and examines the modulation of their properties through the application of biaxial and vertical strain. The findings reveal that all three types of SiC/WS<sub>2</sub> heterojunctions exhibit commendable structural stability. Furthermore, each heterojunction displays direct bandgap semiconductor characteristics, with bandgap energies ranging from 1.392 eV to 1.479 eV. The application of strain systematically influences the electronic properties of the SiC/WS<sub>2</sub> heterojunctions, with the three-layer heterojunction demonstrating heightened sensitivity to strain effects. This three-layer configuration also exhibits enhanced interlayer charge transfer and light absorption capabilities. The superior electronic properties of the SiC/WS<sub>2</sub> heterojunctions underscore their potential utility in electronic and optoelectronic ceramic devices.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115240"},"PeriodicalIF":3.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143844773","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 : 2025-04-15DOI: 10.1016/j.comptc.2025.115241
Ella Tkachenko, Victor Kostjukov
TD-DFT calculations were performed for the colored (MB+) and colorless (МB0) forms of the oxazine dye. The nature of excitation of these forms of dye differs significantly: MB+ undergoes a local excitation, and МB0 has a significant charge transfer. In particular, the dipole moment of MB+ upon excitation slightly decreases while for MB0, on the contrary, it increases almost fourfold. Spatial structures and their photoinduced distortions also differ: while the MB+ chromophore remains flat in both the ground and excited states, MB0 has a significant chromophore kink along the NO line in the ground state and becomes flat in the excited state. The mechanisms of solvatochromic behavior of the dye - non-specific and specific interaction with the solvent - were also analyzed.
{"title":"Excitations of colored and colorless forms of Meldola's blue dye in aqueous solution: A comparative theoretical analysis","authors":"Ella Tkachenko, Victor Kostjukov","doi":"10.1016/j.comptc.2025.115241","DOIUrl":"10.1016/j.comptc.2025.115241","url":null,"abstract":"<div><div>TD-DFT calculations were performed for the colored (MB<sup>+</sup>) and colorless (МB<sup>0</sup>) forms of the oxazine dye. The nature of excitation of these forms of dye differs significantly: MB<sup>+</sup> undergoes a local excitation, and МB<sup>0</sup> has a significant charge transfer. In particular, the dipole moment of MB<sup>+</sup> upon excitation slightly decreases while for MB<sup>0</sup>, on the contrary, it increases almost fourfold. Spatial structures and their photoinduced distortions also differ: while the MB<sup>+</sup> chromophore remains flat in both the ground and excited states, MB<sup>0</sup> has a significant chromophore kink along the N<img>O line in the ground state and becomes flat in the excited state. The mechanisms of solvatochromic behavior of the dye - non-specific and specific interaction with the solvent - were also analyzed.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115241"},"PeriodicalIF":3.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143844770","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 : 2025-04-14DOI: 10.1016/j.comptc.2025.115237
Ali B.M. Ali , Abdulrahman T. Ahmed , Maher Ali Rusho , Suranjana V. Mayani , Suhas Ballal , Rishiv Kalia , Shirin Shomurotova , V. Kavitha , Subhashree Ray , Ahmed M. Naglah
Phosgene (COCl₂) is a highly toxic gas that poses significant risks to human health and the environment, making its detection and monitoring critically important. In this study, we explored the potential of pristine and aluminum-doped biphenylene (BP) monolayers as sensing materials for phosgene detection using the M062X/6-31G(d,p) level of theory. Aluminum doping was shown to disrupt the uniform electronic density of BP, creating active sites that significantly enhance its reactivity. While phosgene adsorption on pristine BP was weak, with an adsorption energy of −6.93 kcal/mol and minimal changes in electronic properties, thermochemical analysis confirmed that this interaction is non-spontaneous under standard conditions. In contrast, Al-doped BP monolayers (Al1-BP and Al2-BP) exhibited strong phosgene adsorption, with adsorption energies of −20.09 kcal/mol and −21.47 kcal/mol, respectively. Notably, a significant change in the energy gap was observed upon phosgene adsorption on the doped monolayers, and the process was found to be thermodynamically favorable, as indicated by negative free energy values. Natural bond orbital (NBO) analysis revealed that the enhanced sensitivity and reactivity of Al-doped BP arise from donor-acceptor interactions between the lone pair electrons of phosgene oxygen and the Rydberg state of lone pairs from the aluminum dopant. These results demonstrate the promising potential of Al-doped BP monolayers as highly sensitive and efficient materials for phosgene detection.
{"title":"Theoretical investigation of Al-doped biphenylene as efficient sensor for phosgene detection","authors":"Ali B.M. Ali , Abdulrahman T. Ahmed , Maher Ali Rusho , Suranjana V. Mayani , Suhas Ballal , Rishiv Kalia , Shirin Shomurotova , V. Kavitha , Subhashree Ray , Ahmed M. Naglah","doi":"10.1016/j.comptc.2025.115237","DOIUrl":"10.1016/j.comptc.2025.115237","url":null,"abstract":"<div><div>Phosgene (COCl₂) is a highly toxic gas that poses significant risks to human health and the environment, making its detection and monitoring critically important. In this study, we explored the potential of pristine and aluminum-doped biphenylene (BP) monolayers as sensing materials for phosgene detection using the M062X/6-31G(d,p) level of theory. Aluminum doping was shown to disrupt the uniform electronic density of BP, creating active sites that significantly enhance its reactivity. While phosgene adsorption on pristine BP was weak, with an adsorption energy of −6.93 kcal/mol and minimal changes in electronic properties, thermochemical analysis confirmed that this interaction is non-spontaneous under standard conditions. In contrast, Al-doped BP monolayers (Al1-BP and Al2-BP) exhibited strong phosgene adsorption, with adsorption energies of −20.09 kcal/mol and −21.47 kcal/mol, respectively. Notably, a significant change in the energy gap was observed upon phosgene adsorption on the doped monolayers, and the process was found to be thermodynamically favorable, as indicated by negative free energy values. Natural bond orbital (NBO) analysis revealed that the enhanced sensitivity and reactivity of Al-doped BP arise from donor-acceptor interactions between the lone pair electrons of phosgene oxygen and the Rydberg state of lone pairs from the aluminum dopant. These results demonstrate the promising potential of Al-doped BP monolayers as highly sensitive and efficient materials for phosgene detection.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115237"},"PeriodicalIF":3.0,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143844771","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 : 2025-04-12DOI: 10.1016/j.comptc.2025.115235
Hai-Chao Ren, Fan Jiang, Xiao-Yang Wu, Bo Wang, Yi-Ping Wang, Jun Tao
This study systematically investigates the structural and decomposition behaviors of hexanitrostilbene (HNS) under high pressures (1 atm–10 GPa) via first-principles calculations and experimental validation. Structural analysis reveals anisotropic compression, with the b-axis exhibiting the highest compressibility (reduced to 83.9 % at 10 GPa), while the c-axis anomalously expands at 3 GPa due to differential hydrogen bond network responses. Electronic structure analysis identifies C–NO₂ bond cleavage as the initial decomposition step, with liberated oxygen atoms competing for CH bonds to form NO and OH radicals. High pressure stabilizes C–-NO₂ bonds by strengthening intermolecular hydrogen interactions, delaying decomposition. Infrared spectroscopy confirms the preservation of trans-HNS configuration under compression. These findings elucidate the interplay between mechanical stress and chemical stability in HNS, providing atomistic insights into its shock insensitivity and guiding the design of advanced energetic materials.
{"title":"Anisotropic structural response and decomposition behaviors of Hexanitrostilbene under high pressure: Insights from ab initio calculations.","authors":"Hai-Chao Ren, Fan Jiang, Xiao-Yang Wu, Bo Wang, Yi-Ping Wang, Jun Tao","doi":"10.1016/j.comptc.2025.115235","DOIUrl":"10.1016/j.comptc.2025.115235","url":null,"abstract":"<div><div>This study systematically investigates the structural and decomposition behaviors of hexanitrostilbene (HNS) under high pressures (1 atm–10 GPa) via first-principles calculations and experimental validation. Structural analysis reveals anisotropic compression, with the <em>b</em>-axis exhibiting the highest compressibility (reduced to 83.9 % at 10 GPa), while the <em>c</em>-axis anomalously expands at 3 GPa due to differential hydrogen bond network responses. Electronic structure analysis identifies C–NO₂ bond cleavage as the initial decomposition step, with liberated oxygen atoms competing for C<img>H bonds to form NO and OH radicals. High pressure stabilizes C–-NO₂ bonds by strengthening intermolecular hydrogen interactions, delaying decomposition. Infrared spectroscopy confirms the preservation of <em>trans</em>-HNS configuration under compression. These findings elucidate the interplay between mechanical stress and chemical stability in HNS, providing atomistic insights into its shock insensitivity and guiding the design of advanced energetic materials.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115235"},"PeriodicalIF":3.0,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143844772","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}
This study analyzes the stability, volume change rate, embedding voltage, lithium ion diffusion, and mechanical properties of Ni, N co-doped LiFePO4 using density functional theory (DFT) calculations. Ni,N doping reduces formation energy to −1.5 eV compared to pristine LiFePO₄, stabilizing the olivine framework during lithiation/de-lithiation. The doping of Ni and N introduces impurity bands, and the band gap before and after doping decreases from 3.71 eV to 1.2 eV, which enhances the electronic conductivity. Meanwhile, the migration barrier is reduced from 0.57 eV to about 0.45 eV and the diffusion coefficient is improved by two orders of magnitude. In addition, nickel doping leads to changes in the local electronic structure, and the reduced electron localization helps the migration of lithium ions. Finally, doping enhances the stiffness, hardness of the material, which further improves its overall performance.
{"title":"Study of electrochemical properties, mechanical properties, and lithium ion diffusion of Ni and N co- doped LiFePO4 based on first principles","authors":"Xinyang Zhao, Fazhan Wang, Kai Jiang, Yumeng Cai, Xiaopeng Li, Haochen Wang, Haizhou Zhang, Lujia Yu","doi":"10.1016/j.comptc.2025.115236","DOIUrl":"10.1016/j.comptc.2025.115236","url":null,"abstract":"<div><div>This study analyzes the stability, volume change rate, embedding voltage, lithium ion diffusion, and mechanical properties of Ni, N co-doped LiFePO<sub>4</sub> using density functional theory (DFT) calculations. Ni,N doping reduces formation energy to −1.5 eV compared to pristine LiFePO₄, stabilizing the olivine framework during lithiation/de-lithiation. The doping of Ni and N introduces impurity bands, and the band gap before and after doping decreases from 3.71 eV to 1.2 eV, which enhances the electronic conductivity. Meanwhile, the migration barrier is reduced from 0.57 eV to about 0.45 eV and the diffusion coefficient is improved by two orders of magnitude. In addition, nickel doping leads to changes in the local electronic structure, and the reduced electron localization helps the migration of lithium ions. Finally, doping enhances the stiffness, hardness of the material, which further improves its overall performance.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115236"},"PeriodicalIF":3.0,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143829243","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 : 2025-04-10DOI: 10.1016/j.comptc.2025.115227
Mohsen Doust Mohammadi , Karwan Wasman Qadir , Hewa Y. Abdullah
This study investigates the adsorption mechanisms and electronic properties of small molecules (CH4, CO, CO2, H2, H2O, N2, NH3, NO, and NO2) on pristine Mg20 and Zn-doped Mg19Zn clusters using advanced computational methods. Density Functional Theory (DFT) calculations with the ωB97XD functional and Def2SVPP basis set were employed to accurately capture dispersion interactions and electronic structure. Cluster geometries were globally optimized using the Artificial Bee Colony algorithm, while Natural Bond Orbital (NBO) analysis and Quantum Theory of Atoms in Molecules (QTAIM) provided insights into charge transfer mechanisms and bonding nature. Non-Covalent Interaction analysis via Reduced Density Gradient (NCI-RDG) and Total Density of States (TDOS) calculations were also performed to examine molecular adsorption effects and Zn doping. The adsorption energy trends revealed significant variation in interaction strengths. Polar and reactive molecules, such as H2O and NO2, exhibited the highest adsorption energies, with NO2 showing the strongest binding at −68.80 kcal·mol−1 (Mg20) and − 72.38 kcal·mol−1 (Mg19Zn). Nonpolar gases like CH4 and H2 demonstrated weak interactions, with adsorption energies ranging from −0.85 to −1.82 kcal·mol−1. The Mg19Zn cluster consistently showed higher adsorption energies, particularly for polar molecules, due to Zn's influence on the electronic properties of the cluster. Electronic property analysis at bond critical points (BCPs) using QTAIM indicated that the interaction type and strength were system-dependent, with stronger covalent and ionic interactions for molecules like H2O, NH3, NO, and NO2. The substitution of Mg with Zn in Mg19Zn enhanced the ionic and polar nature of interactions. These findings highlight the role of cluster composition in modulating adsorption behavior and provide key insights for the design of optimized materials for gas sensing and catalysis applications.
{"title":"A density functional theory investigation of the adsorption of CH4, CO, CO2, H2, H2O, N2, NH3, NO, and NO2 on Mg20 and Mg19Zn clusters","authors":"Mohsen Doust Mohammadi , Karwan Wasman Qadir , Hewa Y. Abdullah","doi":"10.1016/j.comptc.2025.115227","DOIUrl":"10.1016/j.comptc.2025.115227","url":null,"abstract":"<div><div>This study investigates the adsorption mechanisms and electronic properties of small molecules (CH<sub>4</sub>, CO, CO<sub>2</sub>, H<sub>2</sub>, H<sub>2</sub>O, N<sub>2</sub>, NH<sub>3</sub>, NO, and NO<sub>2</sub>) on pristine Mg<sub>20</sub> and Zn-doped Mg<sub>19</sub>Zn clusters using advanced computational methods. Density Functional Theory (DFT) calculations with the ωB97XD functional and Def2SVPP basis set were employed to accurately capture dispersion interactions and electronic structure. Cluster geometries were globally optimized using the Artificial Bee Colony algorithm, while Natural Bond Orbital (NBO) analysis and Quantum Theory of Atoms in Molecules (QTAIM) provided insights into charge transfer mechanisms and bonding nature. Non-Covalent Interaction analysis via Reduced Density Gradient (NCI-RDG) and Total Density of States (TDOS) calculations were also performed to examine molecular adsorption effects and Zn doping. The adsorption energy trends revealed significant variation in interaction strengths. Polar and reactive molecules, such as H<sub>2</sub>O and NO<sub>2</sub>, exhibited the highest adsorption energies, with NO<sub>2</sub> showing the strongest binding at −68.80 kcal·mol<sup>−1</sup> (Mg<sub>20</sub>) and − 72.38 kcal·mol<sup>−1</sup> (Mg<sub>19</sub>Zn). Nonpolar gases like CH<sub>4</sub> and H<sub>2</sub> demonstrated weak interactions, with adsorption energies ranging from −0.85 to −1.82 kcal·mol<sup>−1</sup>. The Mg<sub>19</sub>Zn cluster consistently showed higher adsorption energies, particularly for polar molecules, due to Zn's influence on the electronic properties of the cluster. Electronic property analysis at bond critical points (BCPs) using QTAIM indicated that the interaction type and strength were system-dependent, with stronger covalent and ionic interactions for molecules like H<sub>2</sub>O, NH<sub>3</sub>, NO, and NO<sub>2</sub>. The substitution of Mg with Zn in Mg<sub>19</sub>Zn enhanced the ionic and polar nature of interactions. These findings highlight the role of cluster composition in modulating adsorption behavior and provide key insights for the design of optimized materials for gas sensing and catalysis applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115227"},"PeriodicalIF":3.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143823371","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 : 2025-04-10DOI: 10.1016/j.comptc.2025.115234
Farag M.A. Altalbawy , Shaker Al-Hasnaawei , Prakash Kanjariya , Anjan Kumar , Asha Rajiv , Debasish Shit , Helen Merina Albert , Sumit Pokhriyal
In this work, the structures and electronic properties of CuO and NiO doped MoSe2 nanosheets are investigated using the density functional theory calculations. The structural stability of these metal oxide doped systems was verified using the binding energy analysis, and thus the CuO doped MoSe2 nanosheets are selected for adsorption and sensing of caffeine molecules. The adsorption energies, density of states, charge density difference, work functions and band structures were examined for the adsorption systems. Caffeine molecules are initially positioned on the CuO clusters of the CuO-MoSe2 nanosheets, and after the adsorption, the O and N atoms are strongly adsorbed to the CuO clusters. Based on band structure calculations, CuO and NiO doped MoSe2 nanosheets exhibited semiconductor property and enhanced conductivity because of band gap reduction. These results provide theoretical basis, which is useful in optimizing and developing novel metal oxide doped MoSe2 nanosheets as sensors for caffeine detection.
{"title":"Tuning the electronic and adsorption properties of MoSe2 nanosheets by CuO, NiO and pair CuO-NiO metal oxide doping for efficient sensing of caffeine molecule: A DFT study","authors":"Farag M.A. Altalbawy , Shaker Al-Hasnaawei , Prakash Kanjariya , Anjan Kumar , Asha Rajiv , Debasish Shit , Helen Merina Albert , Sumit Pokhriyal","doi":"10.1016/j.comptc.2025.115234","DOIUrl":"10.1016/j.comptc.2025.115234","url":null,"abstract":"<div><div>In this work, the structures and electronic properties of CuO and NiO doped MoSe<sub>2</sub> nanosheets are investigated using the density functional theory calculations. The structural stability of these metal oxide doped systems was verified using the binding energy analysis, and thus the CuO doped MoSe<sub>2</sub> nanosheets are selected for adsorption and sensing of caffeine molecules. The adsorption energies, density of states, charge density difference, work functions and band structures were examined for the adsorption systems. Caffeine molecules are initially positioned on the CuO clusters of the CuO-MoSe<sub>2</sub> nanosheets, and after the adsorption, the O and N atoms are strongly adsorbed to the CuO clusters. Based on band structure calculations, CuO and NiO doped MoSe<sub>2</sub> nanosheets exhibited semiconductor property and enhanced conductivity because of band gap reduction. These results provide theoretical basis, which is useful in optimizing and developing novel metal oxide doped MoSe<sub>2</sub> nanosheets as sensors for caffeine detection.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115234"},"PeriodicalIF":3.0,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143829242","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 : 2025-04-09DOI: 10.1016/j.comptc.2025.115226
Xin Tan , Zhengyu Liang , Jian Wang , Qiao Yang , Zhanqing He , Hui Qi , Chenglei Yang , Zhiyu Wang
Ytterbium (Yb) doping in diamond has shown promising potential in optoelectronic applications, standing out among rare-earth-doped luminescent materials. In this study, first-principles calculations based on density functional theory (DFT) were employed to investigate the defect structure, electronic structure, and lattice dynamics of the Yb vacancy color center in diamond. We accurately predicted the zero-phonon line (ZPL) energy corresponding to a wavelength of 1003 nm, considering spin-orbit coupling (SOC), a first in such studies. Band structure and density of states calculations revealed the significant influence of Yb’s 4f orbital characteristics on the system's structure. Lattice Dynamics analysis identified two local vibrational modes of Yb at 26 THz, providing new insights into the phonon dynamics and photoluminescence mechanism of the Yb vacancy color center. These findings offer theoretical insights for further exploration of Yb-doped diamond's properties and applications.
{"title":"First-principles calculations of the electronic structure and lattice dynamics of ytterbium (Yb) vacancy color Center in Diamond","authors":"Xin Tan , Zhengyu Liang , Jian Wang , Qiao Yang , Zhanqing He , Hui Qi , Chenglei Yang , Zhiyu Wang","doi":"10.1016/j.comptc.2025.115226","DOIUrl":"10.1016/j.comptc.2025.115226","url":null,"abstract":"<div><div>Ytterbium (Yb) doping in diamond has shown promising potential in optoelectronic applications, standing out among rare-earth-doped luminescent materials. In this study, first-principles calculations based on density functional theory (DFT) were employed to investigate the defect structure, electronic structure, and lattice dynamics of the Yb vacancy color center in diamond. We accurately predicted the zero-phonon line (ZPL) energy corresponding to a wavelength of 1003 nm, considering spin-orbit coupling (SOC), a first in such studies. Band structure and density of states calculations revealed the significant influence of Yb’s 4f orbital characteristics on the system's structure. Lattice Dynamics analysis identified two local vibrational modes of Yb at 26 THz, providing new insights into the phonon dynamics and photoluminescence mechanism of the Yb vacancy color center. These findings offer theoretical insights for further exploration of Yb-doped diamond's properties and applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115226"},"PeriodicalIF":3.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834728","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号