Computational and Theoretical Chemistry最新文献

{"title":"Engineering ORR electrocatalytic performance of single metal site by halogen ligand modification: A first principles perspective","authors":"Shaoqiang Wei ,&nbsp;Lei Li ,&nbsp;Mengjiao Wu ,&nbsp;Huanhuan Wu ,&nbsp;Mengqi Yang ,&nbsp;Min Zhang","doi":"10.1016/j.comptc.2025.115627","DOIUrl":"10.1016/j.comptc.2025.115627","url":null,"abstract":"<div><div>Identifying the well-recognized active sites of single-atom catalysts to modulate the oxygen reduction reaction (ORR) catalytic activity and product selectivity is a challenging problem. In this work, using density functional theory (DFT) calculations, we conducted a systematic study for 3d metal and nitrogen co-doped graphene single-atom catalysts (MN₄), as well as the MN₄ modified by halogen ligand X (MN₄–X). The results indicate that all catalysts, except for ZnN₄ and ZnN₄–X, are thermodynamically and electrochemically stable. The ORR follows the 4e⁻ pathway on Cr/Mn/Fe/CoN₄ and Cr/Mn/Fe/CoN₄–X, while Ni/CuN₄ and Ni/CuN₄–X prefer the 2e⁻ ORR pathway. The X ligand can effectively change the electronic structure of M active site to regulate the adsorption strength for reaction intermediates, thus enhancing the ORR catalytic activity. Notably, CoN₄–Br/I have the lowest 4e⁻ ORR overpotential of about 0.24 V and exhibit superior catalytic activity, significantly outperforming pure Pt catalysts. However, NiN₄–F and CuN₄ respectively with the overpotential of 0.08 and 0.03 V display the excellent 2e⁻ ORR catalytic activity. Furthermore, the O₂ adsorption energy, Bader charge transfer of M atoms, Δ<em>G</em>_⁎OH, and Δ<em>G</em>_⁎OOH were demonstrated to be the descriptors for evaluating the ORR activity and product selectivity. This study provides valuable insights for the design of highly efficient ORR catalysts.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115627"},"PeriodicalIF":3.0,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145747790","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}

{"title":"Unveiling the mechanism of enhanced SO₃ sensing on P-doped T-graphene: The critical roles of donor-acceptor interactions and dopant hybridization","authors":"Qamar Abuhassan ,&nbsp;G. PadmaPriya ,&nbsp;Subhashree Ray ,&nbsp;Amrita Pal ,&nbsp;Vimal Arora ,&nbsp;Ahmed Aldulaimi ,&nbsp;Omayma Salim Waleed ,&nbsp;Rafid Jihad Albadr ,&nbsp;Aseel Smerat ,&nbsp;Akmal Abilkasimov ,&nbsp;Kamoliddin Ziyaev","doi":"10.1016/j.comptc.2025.115649","DOIUrl":"10.1016/j.comptc.2025.115649","url":null,"abstract":"<div><div>Atomistic insights into the impact of elemental doping are crucial for the rational design of high-performance gas sensors based on two-dimensional carbon materials. In this work, we theoretically investigate the influence of nitrogen (N) and phosphorus (P) doping on the sensing properties of T-graphene toward sulfur trioxide (SO₃) using density functional theory at the M062X/6-31 g(d,p) level. Doping significantly alters the monolayer's structural, electronic, and vibrational properties, inducing charge separation. This is evidenced by an increase in the dipole moment from zero in pristine T-graphene to 2.19 Debye and 2.16 Debye for the N- and P-doped systems, respectively. For SO₃ adsorption, interaction with pristine T-graphene is weak physisorption, characterized by a low adsorption energy of −8.82 kcal/mol and negligible charge transfer. Doping substantially enhances reactivity: adsorption energies increase to −10.23 kcal/mol and − 18.49 kcal/mol for the N- and P-doped systems, respectively. This enhancement correlates with a significant change in the energy gap of 9.40 % for N-doping and 27.11 % for P-doping, indicating high sensitivity. Natural Bond Orbital (NBO) analysis further confirms that both doped systems act as charge donors, with calculated charge transfers of 0.13 e and 0.49 e for N- and P-doped T-graphene, respectively.”</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115649"},"PeriodicalIF":3.0,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880326","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}

{"title":"ESIPT process of a chalcone derivative: Electronic structure calculations and nonadiabatic dynamics simulations","authors":"Xin-Yu Zhang,&nbsp;Xue-Tian-Hao Wang,&nbsp;Jia-Jia Huang,&nbsp;Tian-Lan Liao,&nbsp;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":"2026-02-01","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}

{"title":"Stability and photoexcitation of oxygenated polycyclic aromatic hydrocarbons: The influence of water hydrogen-bonds","authors":"José L.F. Santos ,&nbsp;Gabriel L.C. de Souza","doi":"10.1016/j.comptc.2025.115634","DOIUrl":"10.1016/j.comptc.2025.115634","url":null,"abstract":"<div><div>We performed a computational study of the ground state and five lowest excited singlet states of oxygenated polycyclic aromatic hydrocarbons (O-PAHs) derived from phenanthroline: 9,10-phenanthrenequinone, 4,7-phenanthroline-5,6-dione, and 1,10-phenanthroline-5,6-dione. Ground- and excited-state properties were determined using density functional theory (DFT) and time-dependent DFT, respectively, at the CAM-B3LYP/cc-pVTZ level of theory, in both gas phase and aqueous solution. Solvation was modeled through the polarizable continuum model (PCM) and a composite solvation model (CSM) combining explicit water molecules with PCM. Microsolvation stabilized preferential interactions at nitrogen sites and caused the emergence of a bright state in 9,10-phenanthrenequinone, absent in the gas phase. In contrast, 4,7-phenanthroline-5,6-dione and 1,10-phenanthroline-5,6-dione showed no bright states. These findings suggest that the combined presence of a diketone group and nitrogen heteroatoms may exert a significant influence on the photoabsorption process, thereby hindering the photodecomposition of O-PAHs in both the gas phase and aqueous solution, relative to the corresponding polycyclic aromatic hydrocarbons (PAHs) and nitrogen-containing PAHs (N-PAHs).</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115634"},"PeriodicalIF":3.0,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796684","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}

{"title":"Theoretical insights into SOMO–HOMO conversion and luminescence in boracyclic radicals","authors":"Yanbin Zhu,&nbsp;Hongbo Li,&nbsp;Shoufeng Zhang,&nbsp;Jin Zhou,&nbsp;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":"2026-02-01","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}

{"title":"Understanding the aqueous behavior of decanoic acid-based deep eutectic solvents via COSMO-RS and molecular simulations","authors":"Samaneh Barani Pour ,&nbsp;Behie Amirian ,&nbsp;Leyla Bagheri ,&nbsp;Jaber Jahanbin Sardroodi","doi":"10.1016/j.comptc.2025.115608","DOIUrl":"10.1016/j.comptc.2025.115608","url":null,"abstract":"<div><h3>Background</h3><div>Deep eutectic solvents (DESs) based on decanoic acid have emerged as promising green solvents due to their biodegradability and tunable properties. However, their behavior in aqueous environments remains insufficiently understood, limiting their broader application in chemical processes.</div></div><div><h3>Methods</h3><div>COSMO-RS (Conductor-like Screening Model for Real Solvents) calculations, combined with molecular dynamics simulations, were employed to systematically investigate the intermolecular interactions, miscibility, and structural organization of decanoic acid–based deep eutectic solvents in the presence of water. A detailed analysis of thermodynamic descriptors, hydrogen-bonding patterns, and spatial distribution functions was conducted to elucidate the solvent behavior and molecular-level interaction mechanisms governing water – DES systems.</div></div><div><h3>Significant findings</h3><div>The results reveal non-ideal mixing behavior and highlight the critical role of hydrogen bonding and hydrophobic interactions in governing aqueous phase behavior. COSMO-RS predicted partial miscibility trends consistent with simulation results. These insights offer a theoretical foundation for designing water-compatible DES systems for sustainable chemical applications. The interactions between DES components and water molecules were systematically analyzed to understand the solvation effects, hydrogen bonding networks, and structural properties in varying hydration levels. This study examines key properties such as the combined distribution function, spatial distribution function, intermolecular hydrogen bond network, interaction energy, species orientation, density, and self-diffusion coefficients (D_self). Molecular dynamics simulations reveal that increasing the water mass fraction up to 50% weakens the interaction between DES components, significantly impacting their stability and solvation characteristics. These findings provide valuable insights into the behavior of hydrophobic DESs, contributing to their potential applications in pharmaceutical and green chemistry fields.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115608"},"PeriodicalIF":3.0,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691227","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}

{"title":"The AuS monolayer: mechanical anisotropy, strain-tunable optoelectronic properties and high thermoelectric efficiency","authors":"To Toan Thang ,&nbsp;Nguyen Hoang Linh ,&nbsp;Dinh The Hung ,&nbsp;Do Van Truong","doi":"10.1016/j.comptc.2025.115617","DOIUrl":"10.1016/j.comptc.2025.115617","url":null,"abstract":"<div><div>The growing demand for efficient thermoelectric and optoelectronic devices has driven the search for two-dimensional (2D) semiconductors with superior transport and tunable electronic structures. Here, we perform first-principles calculations to explore the structural stability, mechanical anisotropy, and strain-dependent electronic, optical, and thermoelectric properties of the AuS monolayer. The cohesive energy (3.52 eV/atom), phonon spectra, and ab initio molecular dynamics confirm its strong thermodynamic stability. Uniaxial tension reveals pronounced anisotropy with ultimate strengths of 14.62 GPa (<em>ε</em>_<em>xx</em> = 0.28) and 16.76 GPa (<em>ε</em>_<em>yy</em> = 0.34). Unstrained AuS shows an indirect HSE band gap of 2.15 eV, decreasing by 44 % under <em>x</em>-strain, accompanied by red-shifted and enhanced visible–IR absorption (up to 10 times). A favorable electron–hole mass ratio (<em>D</em> = 0.54) enables a peak <em>ZT</em> of 0.71 and a Seebeck coefficient of 2.2 mV/K. These strain-adaptive multifunctional properties make AuS a promising 2D semiconductor for flexible energy-conversion applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115617"},"PeriodicalIF":3.0,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691228","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}

{"title":"Computational characterization of a recently identified disinfection byproduct in drinking water: The chloronitramide anion and its monohydrate complex","authors":"Thufail M. Ismail,&nbsp;Max R. Tucker,&nbsp;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":"2026-02-01","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}

{"title":"Pd-doped GeTe monolayer as a promising gas scavenger upon H2, CO and C2H2 in oil-immersed transformers: a first-principles study","authors":"Shuying Wang","doi":"10.1016/j.comptc.2025.115615","DOIUrl":"10.1016/j.comptc.2025.115615","url":null,"abstract":"<div><div>The reliable operation of oil-immersed transformers is essential for power system stability, where dissolved gas analysis (DGA) has been established as a fundamental diagnostic technique for early fault detection through gas monitoring. This investigation utilizes first-principles calculations to comprehensively evaluate the gas sensing capabilities of a Pd-doped GeTe (Pd-GeTe) monolayer for detecting three dominant dissolved gases—H₂, CO, and C₂H₂—in transformer oil. Our study explores the structural and electronic properties of the doped material, revealing that Pd substitution at Te sites is thermodynamically favorable with a formation energy of −0.65 eV. The adsorption strength hierarchy (CO &gt; C₂H₂ &gt; H₂) correlates directly with calculated adsorption energies of −0.88 eV, −0.49 eV, and − 0.11 eV, respectively, supported by distinct charge transfer values and orbital hybridization patterns. Remarkably, the material demonstrates exceptional sensing responses of −82.66 %, −99.68 %, and − 99.07 % toward H₂, CO and C₂H₂, respectively. Furthermore, recovery time analysis reveals the monolayer's practical reusability. These findings establish Pd-GeTe as a highly promising and reversible sensing platform for DGA applications, providing atomic-level insights into gas-sensing mechanisms and advancing the development of high-performance diagnostic systems for power transformer monitoring.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115615"},"PeriodicalIF":3.0,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691181","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}

{"title":"A computational approach to understand stepwise PCET during hydrogen evolution reaction by iron dithiolene catalyst","authors":"Koushik Makhal ,&nbsp;Bhabani S. Mallik","doi":"10.1016/j.comptc.2025.115564","DOIUrl":"10.1016/j.comptc.2025.115564","url":null,"abstract":"<div><div>We examined the mechanistic insights into hydrogenation and dehydrogenation reactions, encompassing various conceivable pathways of two-electron and two-proton addition reactions catalyzed by redox Fe dithiolene complexes using computational methods. The investigation considers both ligand-mediated and ligand-metal-mediated reaction paths. The plausible pathway for adding two protons and two electrons is the ECEC (E electron transfer process, C proton transfer process) sequence involving protonation at the Fe center and one S center. A decrease in the spin density at the metal center during Fe<img>H bond formation is indicative of electron transfer from the Fe to the hydrogen and sulfur centers. The d orbital of the Fe center is engaged with the s orbital of a hydrogen atom. But the p_y orbital of the sulfur atom interacts with the s orbital of hydrogen, culminating in the formation of an S<img>H bond. In the dehydrogenation reaction, H₂ formation occurs at the Fe<img>H and S<img>H sites.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115564"},"PeriodicalIF":3.0,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145622399","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}