Pub Date : 2025-11-27DOI: 10.1016/j.comptc.2025.115619
Thufail M. Ismail, Max R. Tucker, Gregory S. Tschumper
The chloronitramide anion () was recently identified as disinfection byproduct in drinking water, and various quantum chemistry methods (CCSD(T), MP2, B3LYP, B97XD, and M06-2X) are employed in this study to characterize this negatively charged species and its monohydrate complex. Both vertical and adiabatic quantities indicate the excess electron is bound by 3–4 eV. Four monohydrate minima were identified, each exhibiting double ionic hydrogen bonding. The computed interaction approaches 15 kcal/mol, and it induces pronounced vibrational frequency shifts in both fragments. Natural bond orbital analysis shows a redistribution of negative charge from the anion to HO around 0.02–0.03 .
{"title":"Computational characterization of a recently identified disinfection byproduct in drinking water: The chloronitramide anion and its monohydrate complex","authors":"Thufail M. Ismail, Max R. Tucker, Gregory S. Tschumper","doi":"10.1016/j.comptc.2025.115619","DOIUrl":"10.1016/j.comptc.2025.115619","url":null,"abstract":"<div><div>The chloronitramide anion (<span><math><msup><mrow><msub><mrow><mi>ClNNO</mi></mrow><mrow><mn>2</mn></mrow></msub></mrow><mrow><mo>−</mo></mrow></msup></math></span>) was recently identified as disinfection byproduct in drinking water, and various quantum chemistry methods (CCSD(T), MP2, B3LYP, <span><math><mi>ω</mi></math></span>B97XD, and M06-2X) are employed in this study to characterize this negatively charged species and its monohydrate complex. Both vertical and adiabatic quantities indicate the excess electron is bound by 3–4 eV. Four <span><math><msup><mrow><msub><mrow><mi>ClNNO</mi></mrow><mrow><mn>2</mn></mrow></msub></mrow><mrow><mo>−</mo></mrow></msup></math></span> monohydrate minima were identified, each exhibiting double ionic hydrogen bonding. The computed <span><math><mrow><msup><mrow><msub><mrow><mi>ClNNO</mi></mrow><mrow><mn>2</mn></mrow></msub></mrow><mrow><mo>−</mo></mrow></msup><mo>⋯</mo><msub><mrow><mi>H</mi></mrow><mrow><mn>2</mn></mrow></msub><mi>O</mi></mrow></math></span> interaction approaches 15 kcal/mol, and it induces pronounced vibrational frequency shifts in both fragments. Natural bond orbital analysis shows a redistribution of negative charge from the anion to H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>O around 0.02–0.03 <span><math><mi>e</mi></math></span>.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115619"},"PeriodicalIF":3.0,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691221","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 : 2025-11-26DOI: 10.1016/j.comptc.2025.115607
Amanda D. Torres, Ricardo R. Oliveira, Alexandre B. Rocha
An important class of ligands studied recently is N-heterocyclic carbenes (NHCs) with potential application as a photosensor for solar cells. In this work we investigate organometallic complexes based on (CNC = 2,6-bis[3-isopropylimidazol-2-ylidene]pyridine). We selected metals, namely Co(III), Mn(I) and Cr(0), with the same ligands and applied CASSCF/NEVPT2 and TDDFT methods. It is shown that TDDFT is a suitable method, agreeing well with CASSCF/NEVPT2. The potential for use as a photosensor follows the order: Mn(I), Cr(0), Fe(II), and Co(III). The is shown to the best candidates for photosensitizer due to the higher absorption band in the region of maximum solar radiation and most effective intersystem crossing (ISC) to the triplet state, followed very closely by .
{"title":"Electronic spectra simulations of selected d6 NHC-metal complexes for photosensors applications","authors":"Amanda D. Torres, Ricardo R. Oliveira, Alexandre B. Rocha","doi":"10.1016/j.comptc.2025.115607","DOIUrl":"10.1016/j.comptc.2025.115607","url":null,"abstract":"<div><div>An important class of ligands studied recently is N-heterocyclic carbenes (NHCs) with potential application as a photosensor for solar cells. In this work we investigate organometallic complexes based on <figure><img></figure> (CNC = 2,6-bis[3-isopropylimidazol-2-ylidene]pyridine). We selected <span><math><msup><mrow><mi>d</mi></mrow><mrow><mn>6</mn></mrow></msup></math></span> metals, namely Co(III), Mn(I) and Cr(0), with the same ligands and applied CASSCF/NEVPT2 and TDDFT methods. It is shown that TDDFT is a suitable method, agreeing well with CASSCF/NEVPT2. The potential for use as a photosensor follows the order: Mn(I), Cr(0), Fe(II), and Co(III). The <figure><img></figure> is shown to the best candidates for photosensitizer due to the higher absorption band in the region of maximum solar radiation and most effective intersystem crossing (ISC) to the triplet state, followed very closely by <figure><img></figure> .</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115607"},"PeriodicalIF":3.0,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145622403","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}
Chalcone derivatives which include excited-state intramolecular proton transfer (ESIPT) processes have attracted much attention due to their potential applications as photochromic materials. Herein, static electronic structure calculations and non-adiabatic dynamics simulations were employed to investigate the ESIPT mechanism and the excited-state decay behavior of an ESIPT-active chalcone fluorescent probe (o-HCAMI). Two distinct excited-state deactivation pathways were identified. About 98.6 % of the trajectories successfully returned to the ground state via the first pathway with efficient ESIPT process during 1 ps simulation time. In the meantime, only 1.4 % of the trajectories underwent a non-radiative jump via the second path without the ESIPT process. The average excited-state lifetime was estimated to be 426.7 fs. In conclusion, we propose the excited-state deactivation mechanism of chalcone derivative system in vacuum, which will provide insights for the rational design of ESIPT-driven photochromic materials.
{"title":"ESIPT process of a chalcone derivative: Electronic structure calculations and nonadiabatic dynamics simulations","authors":"Xin-Yu Zhang, Xue-Tian-Hao Wang, Jia-Jia Huang, Tian-Lan Liao, Shu-Hua Xia","doi":"10.1016/j.comptc.2025.115602","DOIUrl":"10.1016/j.comptc.2025.115602","url":null,"abstract":"<div><div>Chalcone derivatives which include excited-state intramolecular proton transfer (ESIPT) processes have attracted much attention due to their potential applications as photochromic materials. Herein, static electronic structure calculations and non-adiabatic dynamics simulations were employed to investigate the ESIPT mechanism and the excited-state decay behavior of an ESIPT-active chalcone fluorescent probe (<em>o-HCAMI</em>). Two distinct excited-state deactivation pathways were identified. About 98.6 % of the trajectories successfully returned to the ground state via the first pathway with efficient ESIPT process during 1 ps simulation time. In the meantime, only 1.4 % of the trajectories underwent a non-radiative jump via the second path without the ESIPT process. The average excited-state lifetime was estimated to be 426.7 fs. In conclusion, we propose the excited-state deactivation mechanism of chalcone derivative system in vacuum, which will provide insights for the rational design of ESIPT-driven photochromic materials.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115602"},"PeriodicalIF":3.0,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145622404","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 : 2025-11-21DOI: 10.1016/j.comptc.2025.115600
Huan Wang , Changli Shi , Zihe Cao , Xiaolu Chen , Qiguo Zhang , Gangjun Gong , Qiang Lu , Xinhua Yuan , Bing Zhang
MgNi alloys are promising candidates for hydrogen storage materials due to their significant potential in sustainable energy technologies. However, accurately predicting hydrogen adsorption energies and identifying optimal storage sites remain critical challenges. This study evaluates the performance of two DFT exchange-correlation functionals (PBE and SCAN) and assesses the effects of Hubbard U correction and van der Waals interaction on MgNi alloys. The results demonstrate that SCAN significantly outperforms PBE in predicting hydrogen adsorption energies due to its consideration of orbital kinetic energy density. Variations in the contributions of Hubbard U and vdW interactions are observed across different storage sites. Based on parameters such as volume change rate, adsorption energy, NiH bond length and ICOHP, the H2 site is identified as the preferred storage site. These findings highlight the importance of theoretical parameters in optimizing MgNi alloy systems, providing insights for advancing efficient hydrogen storage materials and supporting sustainable energy technologies.
MgNi合金因其在可持续能源技术中的巨大潜力而成为储氢材料的有希望的候选者。然而，准确预测氢吸附能和确定最佳储存地点仍然是关键的挑战。本研究评估了两种DFT交换相关泛函（PBE和SCAN）的性能，并评估了Hubbard U校正和van der Waals相互作用对MgNi合金的影响。结果表明，由于考虑了轨道动能密度，SCAN在预测氢吸附能方面明显优于PBE。在不同的储存地点观察到Hubbard U和vdW相互作用的贡献的变化。基于体积变化率、吸附能、NiH键长、ICOHP等参数，确定H2位点为首选存储位点。这些发现突出了理论参数在优化MgNi合金系统中的重要性，为推进高效储氢材料和支持可持续能源技术提供了见解。
{"title":"First-principles study of hydrogen adsorption energy and preferred storage site in MgNi alloys","authors":"Huan Wang , Changli Shi , Zihe Cao , Xiaolu Chen , Qiguo Zhang , Gangjun Gong , Qiang Lu , Xinhua Yuan , Bing Zhang","doi":"10.1016/j.comptc.2025.115600","DOIUrl":"10.1016/j.comptc.2025.115600","url":null,"abstract":"<div><div>Mg<img>Ni alloys are promising candidates for hydrogen storage materials due to their significant potential in sustainable energy technologies. However, accurately predicting hydrogen adsorption energies and identifying optimal storage sites remain critical challenges. This study evaluates the performance of two DFT exchange-correlation functionals (PBE and SCAN) and assesses the effects of Hubbard U correction and van der Waals interaction on Mg<img>Ni alloys. The results demonstrate that SCAN significantly outperforms PBE in predicting hydrogen adsorption energies due to its consideration of orbital kinetic energy density. Variations in the contributions of Hubbard U and vdW interactions are observed across different storage sites. Based on parameters such as volume change rate, adsorption energy, Ni<img>H bond length and ICOHP, the H2 site is identified as the preferred storage site. These findings highlight the importance of theoretical parameters in optimizing Mg<img>Ni alloy systems, providing insights for advancing efficient hydrogen storage materials and supporting sustainable energy technologies.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115600"},"PeriodicalIF":3.0,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691225","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 : 2025-11-20DOI: 10.1016/j.comptc.2025.115599
Xiaoyan Cao , Michael Dolg
A systematic quantum chemical investigation was conducted at the density functional theory level, employing relativistic pseudopotentials for Hg, Pb, and U, to investigate the detoxification from heavy metal ions (M2+ = Hg2+, Pb2+, and UO22+) using the chelator combination of H₂BAL (British Anti-Lewisite) and H₄DMSA (meso-dimercaptosuccinic acid). Target compounds for detoxification included model systems of a classical zinc-finger protein (ZnF) and calmodulin (CaM), where Zn2+and Ca2+ were replaced by a poisonous M2+ ion, i.e., Hg2+-ZnF, Pb2+-ZnF, Pb2+-CaM, and UO22+-CaM. It was found that M2+ coordinates with up to two DMSA units to form stable complexes, whereas for BAL the coordination numbers were two for Hg2+ and Pb2+, and four for UO22+. The calculated negative changes of Gibbs free energies ΔG in the metal-ligand exchange reactions between M2+-ZnF and neutral/anionic BAL indicate thermodynamically spontaneous processes. Our results demonstrate that the H2BAL/H4DMSA combination might be a promising strategy for uranyl (UO22+) detoxification.
{"title":"Quantum chemical studies on chelator combination in Hg2+, Pb2+ and UO22+ poisonings","authors":"Xiaoyan Cao , Michael Dolg","doi":"10.1016/j.comptc.2025.115599","DOIUrl":"10.1016/j.comptc.2025.115599","url":null,"abstract":"<div><div>A systematic quantum chemical investigation was conducted at the density functional theory level, employing relativistic pseudopotentials for Hg, Pb, and U, to investigate the detoxification from heavy metal ions (M<sup>2+</sup> = Hg<sup>2+</sup>, Pb<sup>2+</sup>, and UO<sub>2</sub><sup>2+</sup>) using the chelator combination of H₂BAL (British Anti-Lewisite) and H₄DMSA (meso-dimercaptosuccinic acid). Target compounds for detoxification included model systems of a classical zinc-finger protein (ZnF) and calmodulin (CaM), where Zn<sup>2+</sup>and Ca<sup>2+</sup> were replaced by a poisonous M<sup>2+</sup> ion, i.e., Hg<sup>2+</sup>-ZnF, Pb<sup>2+</sup>-ZnF, Pb<sup>2+</sup>-CaM, and UO<sub>2</sub><sup>2+</sup>-CaM. It was found that M<sup>2+</sup> coordinates with up to two DMSA units to form stable complexes, whereas for BAL the coordination numbers were two for Hg<sup>2+</sup> and Pb<sup>2+</sup>, and four for UO<sub>2</sub><sup>2+</sup>. The calculated negative changes of Gibbs free energies ΔG in the metal-ligand exchange reactions between M<sup>2+</sup>-ZnF and neutral/anionic BAL indicate thermodynamically spontaneous processes. Our results demonstrate that the H<sub>2</sub>BAL/H<sub>4</sub>DMSA combination might be a promising strategy for uranyl (UO<sub>2</sub><sup>2+</sup>) detoxification.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115599"},"PeriodicalIF":3.0,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145578656","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 : 2025-11-19DOI: 10.1016/j.comptc.2025.115590
Lachlan O. Smith, Deborah L. Crittenden
Design of redox-active species for applications such as sensing and energy storage requires reliable prediction of redox potentials, frequently in protic environments. However, this is complicated by the fact that multiple reaction pathways are possible, which cannot be easily elucidated experimentally. Computational assignment of redox reaction mechanisms by matching computed and measured redox potentials is an enticing possibility, but demands careful treatment of computational uncertainties because these may be of the same order of magnitude as mechanism-dependent differences. Here, we introduce a new scheme for estimating computational “error bars” by identifying density functionals whose predicted redox potentials systematically bound experimental data. We demonstrate that the bounding behaviour of hybrid functionals may be tuned by altering the proportion of Hartree–Fock exchange, while generalised gradient functionals are more sensitive to the nature and form of the specific gradient corrections applied to correct for the local density approximation.
{"title":"Predicting protic redox potentials with computational error bars","authors":"Lachlan O. Smith, Deborah L. Crittenden","doi":"10.1016/j.comptc.2025.115590","DOIUrl":"10.1016/j.comptc.2025.115590","url":null,"abstract":"<div><div>Design of redox-active species for applications such as sensing and energy storage requires reliable prediction of redox potentials, frequently in protic environments. However, this is complicated by the fact that multiple reaction pathways are possible, which cannot be easily elucidated experimentally. Computational assignment of redox reaction mechanisms by matching computed and measured redox potentials is an enticing possibility, but demands careful treatment of computational uncertainties because these may be of the same order of magnitude as mechanism-dependent differences. Here, we introduce a new scheme for estimating computational “error bars” by identifying density functionals whose predicted redox potentials systematically bound experimental data. We demonstrate that the bounding behaviour of hybrid functionals may be tuned by altering the proportion of Hartree–Fock exchange, while generalised gradient functionals are more sensitive to the nature and form of the specific gradient corrections applied to correct for the local density approximation.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115590"},"PeriodicalIF":3.0,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576690","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 : 2025-11-19DOI: 10.1016/j.comptc.2025.115592
Yanbin Zhu, Hongbo Li, Shoufeng Zhang, Jin Zhou, Li Zhang
Luminescent radicals exhibiting SOMO–HOMO conversion (SHC) have attracted considerable interest due to their distinctive photophysical properties. This work presents a computational study on a series of boracyclic-based radicals, exploring how π-conjugation and electron-donating/withdrawing groups tune electronic structure and radiative and nonradiative decay rates. Calculations reveal that all designed radicals display SHC behavior, with luminescence originating from the D₁ state. Natural Bond Orbital (NBO) and Atoms-in-Molecules (AIM) analyses indicate pronounced intramolecular charge transfer (ICT) and noncovalent interactions stabilized by boron–oxygen coordination. Electron-donating substituents enhance electron delocalization, promoting radical aromaticity and stability. In contrast, nonradiative decay is modulated by structural relaxation and hybridized charge-transfer and local excitation (CT–LE) states. These results underscore the critical role of π-conjugation, number of boracyclic units, and substituent electronic nature in tuning electronic properties and recombination processes. The insights offer guidelines for enhancing photostability and broadening photofunctionality in radical-based luminescent systems.
{"title":"Theoretical insights into SOMO–HOMO conversion and luminescence in boracyclic radicals","authors":"Yanbin Zhu, Hongbo Li, Shoufeng Zhang, Jin Zhou, Li Zhang","doi":"10.1016/j.comptc.2025.115592","DOIUrl":"10.1016/j.comptc.2025.115592","url":null,"abstract":"<div><div>Luminescent radicals exhibiting SOMO–HOMO conversion (SHC) have attracted considerable interest due to their distinctive photophysical properties. This work presents a computational study on a series of boracyclic-based radicals, exploring how π-conjugation and electron-donating/withdrawing groups tune electronic structure and radiative and nonradiative decay rates. Calculations reveal that all designed radicals display SHC behavior, with luminescence originating from the D₁ state. Natural Bond Orbital (NBO) and Atoms-in-Molecules (AIM) analyses indicate pronounced intramolecular charge transfer (ICT) and noncovalent interactions stabilized by boron–oxygen coordination. Electron-donating substituents enhance electron delocalization, promoting radical aromaticity and stability. In contrast, nonradiative decay is modulated by structural relaxation and hybridized charge-transfer and local excitation (CT–LE) states. These results underscore the critical role of π-conjugation, number of boracyclic units, and substituent electronic nature in tuning electronic properties and recombination processes. The insights offer guidelines for enhancing photostability and broadening photofunctionality in radical-based luminescent systems.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115592"},"PeriodicalIF":3.0,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145578655","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 paper reports a Density Functional Theory (“DFT”) assessment of “CaO”, “MgO”, and “BeO” nanocages for acrolein (“AC”) detection, analyzing various adsorption configurations and Frontier Molecular Orbital (“FMO”) variations. The calculated interaction strength follows the order “AC”@”CaO" > “AC”@”MgO" > “AC”@”BeO". Electrical conductivity analysis reveals that the “BeO” nanocage possesses the maximum conductivity, surpassing “MgO” and “CaO”. The optimization of “AC” desorption recovery time was also performed. Crucially, the analysis of complexes in different media demonstrated that structural stability is significantly higher in aqueous media (ΔG_W analysis) compared to the oily phase (ΔG_O), confirming efficient capture across gaseous, aqueous, and oily phases. The investigation of “HOMO-LUMO" levels and the energy gap further substantiates the viability of these oxide nanocages as high-performance sensors for toxic “AC” molecules.
{"title":"Acrolein detection in gaseous, aqueous, and oil phases through CaO, MgO, and BeO nanocages based on DFT","authors":"Khalid Mujasam Batoo , Pawan Sharma , Muhammad Farzik Ijaz , Abhishek Kumar , Syeda Wajida Kazmi , Forat H. Alsultany , Iman Samir Alalaq , Ruaa Sattar , Munthir Abdulwahid Abdulhussain , Merwa Alhadrawi","doi":"10.1016/j.comptc.2025.115594","DOIUrl":"10.1016/j.comptc.2025.115594","url":null,"abstract":"<div><div>This paper reports a Density Functional Theory (“DFT”) assessment of “CaO”, “MgO”, and “BeO” nanocages for acrolein (“AC”) detection, analyzing various adsorption configurations and Frontier Molecular Orbital (“FMO”) variations. The calculated interaction strength follows the order “AC”@”CaO\" > “AC”@”MgO\" > “AC”@”BeO\". Electrical conductivity analysis reveals that the “BeO” nanocage possesses the maximum conductivity, surpassing “MgO” and “CaO”. The optimization of “AC” desorption recovery time was also performed. Crucially, the analysis of complexes in different media demonstrated that structural stability is significantly higher in aqueous media (ΔG_W analysis) compared to the oily phase (ΔG_O), confirming efficient capture across gaseous, aqueous, and oily phases. The investigation of “HOMO-LUMO\" levels and the energy gap further substantiates the viability of these oxide nanocages as high-performance sensors for toxic “AC” molecules.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115594"},"PeriodicalIF":3.0,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145747792","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 : 2025-11-17DOI: 10.1016/j.comptc.2025.115596
Jerimiah A. Zamora, Michelle L. Pantoya, Adelia J.A. Aquino
This work models the interaction of Ga, In, and Hg with the nitroaromatic explosive 2,4,6-trinitrotolulene (TNT) using density functional theory (DFT). The electronic properties of Ga and In are hypothesized to destabilize TNT and may induce decomposition when in atomic scale proximity. TNT configurations (monomer, dimer, and trimer) were examined. The formation energies (ΔEf), enthalpies (ΔHf), and Gibbs free energies (ΔGf), energy gap (Δε), charge analysis (NPA), deformation energies (Ed), stabilization energy (E(2)), and weak interaction (NCI) are computed for all complexes. Ga-(TNT)n and In-(TNT)n complexes show enhanced reactivity across all configurations, with decreasing energy gaps as n increases, consistent with prior DFT studies on Al–TNT complexes. NPA, E(2), and NCI analyses indicate charge transfer, orbital overlap, and steric effects driving Ga and In complexes formation, but not for Hg. Overall, thermodynamic results suggest Ga and In may destabilize TNT, offering potential for applications that neutralize its explosive potential.
{"title":"Exploring the stability and reactivity of Ga, In, and Hg interactions with TNT: Insights from DFT calculations","authors":"Jerimiah A. Zamora, Michelle L. Pantoya, Adelia J.A. Aquino","doi":"10.1016/j.comptc.2025.115596","DOIUrl":"10.1016/j.comptc.2025.115596","url":null,"abstract":"<div><div>This work models the interaction of Ga, In, and Hg with the nitroaromatic explosive 2,4,6-trinitrotolulene (TNT) using density functional theory (DFT). The electronic properties of Ga and In are hypothesized to destabilize TNT and may induce decomposition when in atomic scale proximity. TNT configurations (monomer, dimer, and trimer) were examined. The formation energies (ΔE<sub>f</sub>), enthalpies (ΔH<sub>f</sub>), and Gibbs free energies (ΔG<sub>f</sub>), energy gap (Δε), charge analysis (NPA), deformation energies (E<sub>d</sub>), stabilization energy (E<sup>(2)</sup>), and weak interaction (NCI) are computed for all complexes. Ga-(TNT)<sub>n</sub> and In-(TNT)<sub>n</sub> complexes show enhanced reactivity across all configurations, with decreasing energy gaps as n increases, consistent with prior DFT studies on Al–TNT complexes. NPA, E<sup>(2)</sup>, and NCI analyses indicate charge transfer, orbital overlap, and steric effects driving Ga and In complexes formation, but not for Hg. Overall, thermodynamic results suggest Ga and In may destabilize TNT, offering potential for applications that neutralize its explosive potential.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115596"},"PeriodicalIF":3.0,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145578654","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 : 2025-11-14DOI: 10.1016/j.comptc.2025.115598
Liang Song , Ze-Chun Lin , Xing-Long Chen , Yun-Hui Hou , Min Li , Xiao Ma , Tao Fang , Fang-Chao Hou , Jing Sun
The oxidation behavior of SWCNTs by O2 was examined using the ReaxFF molecular dynamics simulations. Results show that cap-ends serve as preferred targets for the attack of O2 molecules due to their high curvature and exposed carbon atoms. Local oxidation of SWCNT ends leads to the formation of metastable pores and epoxy groups, making it challenging for the end cap to close and restructure. As the temperature rises to 4750–5250 K, Y-shaped carbon chain nodes spontaneously rearrange into 5-membered rings. This ring condensation gradually facilitates the closure of the hemispherical carbon cap, although oxygen depletion limits extensive reconstruction. An increase in O2 concentration promotes the accumulation of carbonyl and epoxy groups. CO emerges as the dominant small molecule product, with its yield increasing in tandem with temperature and oxygen concentration. In contrast, the amount of CO2 formed is minimal and occurs only in (16,16) SWCNTs.
{"title":"Atomic-level insights into the oxidation of SWCNTs based on reactive molecular dynamics simulations","authors":"Liang Song , Ze-Chun Lin , Xing-Long Chen , Yun-Hui Hou , Min Li , Xiao Ma , Tao Fang , Fang-Chao Hou , Jing Sun","doi":"10.1016/j.comptc.2025.115598","DOIUrl":"10.1016/j.comptc.2025.115598","url":null,"abstract":"<div><div>The oxidation behavior of SWCNTs by O<sub>2</sub> was examined using the ReaxFF molecular dynamics simulations. Results show that cap-ends serve as preferred targets for the attack of O<sub>2</sub> molecules due to their high curvature and exposed carbon atoms. Local oxidation of SWCNT ends leads to the formation of metastable pores and epoxy groups, making it challenging for the end cap to close and restructure. As the temperature rises to 4750–5250 K, Y-shaped carbon chain nodes spontaneously rearrange into 5-membered rings. This ring condensation gradually facilitates the closure of the hemispherical carbon cap, although oxygen depletion limits extensive reconstruction. An increase in O<sub>2</sub> concentration promotes the accumulation of carbonyl and epoxy groups. CO emerges as the dominant small molecule product, with its yield increasing in tandem with temperature and oxygen concentration. In contrast, the amount of CO<sub>2</sub> formed is minimal and occurs only in (16,16) SWCNTs.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115598"},"PeriodicalIF":3.0,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576691","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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