Computational and Theoretical Chemistry最新文献_第4页

Iridium(III) complex donors for triplet-material-based organic photovoltaics: a theoretical design strategy for enhanced charge separation 基于三重材料的有机光伏电池的铱（III）复合物供体：一种增强电荷分离的理论设计策略

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2026-03-01 Epub Date: 2026-01-24 DOI: 10.1016/j.comptc.2026.115690

Shuangbao Li , Lingfeng Sheng , Zi'an Wang , Yang Chen , Zhongmin Su

{"title":"Iridium(III) complex donors for triplet-material-based organic photovoltaics: a theoretical design strategy for enhanced charge separation","authors":"Shuangbao Li , Lingfeng Sheng , Zi'an Wang , Yang Chen , Zhongmin Su","doi":"10.1016/j.comptc.2026.115690","DOIUrl":"10.1016/j.comptc.2026.115690","url":null,"abstract":"<div><div>Metallated triplet materials can boost the power conversion efficiency of organic photovoltaics owing to their long-lived and tunable triplet excitons. However, their development is hampered by unclear triplet dynamics and a lack of systematic structure-property relationship studies. To address these challenges, this study presents a series of new Ir(III) complex donors (<strong>1</strong>–<strong>5</strong>), engineered by inserting strong electron-withdrawing moieties into the report TBzIr skeleton. DFT and TD-DFT calculations reveal that this design extends π-conjugation, enhances charge separation, and preserves favorable triplet exciton dynamics. Notably, molecules <strong>3–5</strong> show a highly efficient S<sub>1</sub> → T<sub>5</sub> intersystem crossing pathway. Furthermore, the <strong>4</strong>/Y6 system demonstrates optimized molecular torsion that reduces intermolecular Coulomb binding, promoting charge dissociation and transport. With enhanced intersystem crossing and suppressed triplet recombination, molecule <strong>4</strong> emerges as a highly promising donor for triplet-material-based organic photovoltaics (T-OPVs). This work elucidates key structure-property relationships and provides a strategic design framework for developing high-efficiency T-OPV.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115690"},"PeriodicalIF":3.0,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073809","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}

引用次数: 0

The effects of size and second metal doping of copper-based core-shell catalysts on methanol dehydrogenation to methyl formate 铜基核壳催化剂尺寸及二次金属掺杂对甲醇脱氢制甲酸甲酯的影响

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2026-03-01 Epub Date: 2026-01-24 DOI: 10.1016/j.comptc.2026.115692

Xuhui Wang , Jiahui Qi , Jun Ren , Chaoyang Gao , Yiwei Su

{"title":"The effects of size and second metal doping of copper-based core-shell catalysts on methanol dehydrogenation to methyl formate","authors":"Xuhui Wang , Jiahui Qi , Jun Ren , Chaoyang Gao , Yiwei Su","doi":"10.1016/j.comptc.2026.115692","DOIUrl":"10.1016/j.comptc.2026.115692","url":null,"abstract":"<div><div>Copper-based core-shell catalyst is a promising way to improve the catalytic activity for methanol dehydrogenation to methyl formate (MF), but the size effect remains unknown. Cu<sub>13</sub>, Cu<sub>38</sub>, Cu<sub>55</sub> catalysts have been constructed to systematically investigate the reaction mechanism of methyl formate (MF) generation by using density functional theory (DFT) calculations. The results show that the order of catalytic activity is Cu<sub>13</sub> > Cu<sub>38</sub> > Cu<sub>55</sub>, confirmed by the results of d-band center and kinetic analysis. Moreover, Cu<sub>13</sub> catalyst with optimal performance was subjected to the second-metal (Zn, Ni and Pd) core doping and shell doping, respectively, resulting in the construction of six doping models. This research reveals a normal distribution relationship between the d-band center and free energy barrier for six doped catalysts, and Ni-doped into shell catalysts exhibit excellent catalytic performance, attributing to the closer distance between the d-band center and Fermi level. Additionally, the reaction rate constant is always higher than that on other catalysts at the same temperature, accelerating the reaction process of methanol dehydrogenation to MF. This work provides a theoretical reference for the design and development of copper-based catalysts with a core-shell structure.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115692"},"PeriodicalIF":3.0,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073808","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}

引用次数: 0

The reactive fingerprint of toxic alkylphenols: Insights from NO+ chemical ionization and spectroscopy 有毒烷基酚的反应指纹图谱：来自NO+化学电离和光谱学的见解

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2026-03-01 Epub Date: 2026-01-15 DOI: 10.1016/j.comptc.2026.115682

Manjeet Bhatia

{"title":"The reactive fingerprint of toxic alkylphenols: Insights from NO+ chemical ionization and spectroscopy","authors":"Manjeet Bhatia","doi":"10.1016/j.comptc.2026.115682","DOIUrl":"10.1016/j.comptc.2026.115682","url":null,"abstract":"<div><div>Alkylphenols, which consist of a phenolic ring attached to an alkyl chain, are widely used in industrial processes and consumer products, including food-contact materials such as plastic containers. Their broad application raises concerns regarding human exposure and environmental impact. In this work, density functional theory (DFT) was employed to investigate the electronic structure and chemical reactivity of alkylphenols using different DFT functionals. The key molecular descriptors, including ionization energy, electron affinity, HOMO–LUMO gap, and global reactivity parameters, were systematically evaluated. Excited-state properties and UV–Vis absorption spectra were further examined through time-dependent DFT (TD-DFT). The potential of NO<span><math><msup><mrow></mrow><mrow><mo>+</mo></mrow></msup></math></span> as a reagent ion was also explored through charge transfer and H<span><math><msup><mrow></mrow><mrow><mo>−</mo></mrow></msup></math></span> abstraction reactions. Benchmark DFT calculations confirm that B3LYP/6-311++G(d, p) is well-suited for ground-state studies, and further evaluations demonstrate that NO<span><math><msup><mrow></mrow><mrow><mo>+</mo></mrow></msup></math></span> readily undergoes exothermic charge transfer with alkylphenols, proceeding at collision-controlled rates. In contrast, hydride abstraction is endothermic, and association pathways are not favorable. These findings underscore the potential of NO<span><math><msup><mrow></mrow><mrow><mo>+</mo></mrow></msup></math></span>-based chemical ionization mass spectrometry (CIMS) techniques, such as PTR-MS and SIFT-MS, for the sensitive detection and quantification of alkylphenols. Overall, this comprehensive computational study provides valuable insights into the stability, reactivity, and photophysical behavior of alkylphenols, advancing their identification in both environmental monitoring and human health risk assessments.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115682"},"PeriodicalIF":3.0,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974360","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}

引用次数: 0

Research on the performance optimization of Y2Te3 thermoelectric materials based on strain engineering 基于应变工程的Y2Te3热电材料性能优化研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2026-03-01 Epub Date: 2026-01-10 DOI: 10.1016/j.comptc.2026.115677

Xinyue Zhang , Zhenqing Yang , Wansong Zhang, Changjin Shao, Yuhong Xia, Haoru Zhang, Chundan Lin

{"title":"Research on the performance optimization of Y2Te3 thermoelectric materials based on strain engineering","authors":"Xinyue Zhang , Zhenqing Yang , Wansong Zhang, Changjin Shao, Yuhong Xia, Haoru Zhang, Chundan Lin","doi":"10.1016/j.comptc.2026.115677","DOIUrl":"10.1016/j.comptc.2026.115677","url":null,"abstract":"<div><div>Advanced thermoelectric materials play a pivotal role in waste heat recovery. In this study, we systematically investigated the thermoelectric regulation mechanism of rare-earth chalcogenide Y<sub>2</sub>Te<sub>3</sub> under axial strain using first-principles calculations combined with semi-classical Boltzmann transport theory. Our results demonstrate that at room temperature (300<em>K</em>), Y<sub>2</sub>Te<sub>3</sub> exhibits superior thermoelectric performance along the c-axis. After strain optimization, the maximum power factors for p-type and n-type Y<sub>2</sub>Te<sub>3</sub> reach 1.4 mW·m<sup>−1</sup>·K<sup>−2</sup> and 14 mW·m<sup>−1</sup>·K<sup>−2</sup>, respectively, while the thermoelectric figure of merit (<em>ZT</em>) increases to 0.17 and 1.05, respectively. Benefiting from its inherently low lattice thermal conductivity, the <em>ZT</em> values of p-type and n-type Y<sub>2</sub>Te<sub>3</sub> further increase to 0.52 and 2.1 at 800 K, respectively. This study not only highlights the outstanding thermoelectric properties of Y<sub>2</sub>Te<sub>3</sub> but also underscores the substantial enhancement achieved through strain engineering, offering novel insights and theoretical support for the thermoelectric applications of rare-earth chalcogenides.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115677"},"PeriodicalIF":3.0,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974359","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}

引用次数: 0

Semiconducting Behavior, Structural Stability, and Optical Response of XGaGeH (X = Ca, Sr) Hydrides: A DFT Study XGaGeH （X = Ca, Sr）氢化物的半导体行为、结构稳定性和光学响应：DFT研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2026-03-01 Epub Date: 2026-01-19 DOI: 10.1016/j.comptc.2026.115679

L. Boughlima , A. Jabar , L. Bahmad , R. Ahl Laamara

引用次数: 0

Structural evolution and thermodynamic tuning of Sr₁₋ₓBaₓLiH₃: Inverse perovskites for high-volumetric-capacity hydrogen storage Sr₁₀ₓBaₓLiH₃：大容量储氢用逆钙钛矿的结构演化与热力学调整

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2026-03-01 Epub Date: 2026-01-11 DOI: 10.1016/j.comptc.2026.115663

S. Saadoun , T. Ghellab , H. Baaziz , T. Saadi , Z. .Charifi

{"title":"Structural evolution and thermodynamic tuning of Sr₁₋ₓBaₓLiH₃: Inverse perovskites for high-volumetric-capacity hydrogen storage","authors":"S. Saadoun , T. Ghellab , H. Baaziz , T. Saadi , Z. .Charifi","doi":"10.1016/j.comptc.2026.115663","DOIUrl":"10.1016/j.comptc.2026.115663","url":null,"abstract":"<div><div>This computational study investigates the structure-property relationships in Sr₁₋ₓBaₓLiH₃ (0 ≤ x ≤ 1) inverse perovskite hydrides using DFT. We demonstrate how controlled Ba substitution systematically tunes formation energies (−60.4 to −58.8 kJ/mol·H₂) and hydrogen binding energies (−1.19 to −1.24 eV), enabling precise optimization of hydrogen storage performance. The alloys exhibit an unusual structural evolution from cubic (<span><math><mi>Pm</mi><mover><mn>3</mn><mo>¯</mo></mover><mi>m</mi></math></span>) to tetragonal (<em>P4/mmm</em>) and back to cubic (<span><math><mi>Pm</mi><mover><mn>3</mn><mo>¯</mo></mover><mi>m</mi></math></span>) symmetry, with the re-entrant cubic phase at x = 0.875 showing exceptional stability (cohesive energy −17.1 eV). Electronic structure calculations reveal composition-dependent bandgap transitions (3.45–4.13 eV, mBJ-GGA) that alternate between direct and indirect character. For hydrogen storage, the materials' key advantage lies in their outstanding volumetric capacity of 188 g H₂/L, which significantly exceeds the capacities of many benchmark storage systems, while they maintain a moderate gravimetric capacity of 2.1–3.2 wt%. Desorption temperatures (449–462 K) are directly correlated with the hydrogen binding energy landscape. The study identifies an optimal composition window (<em>x</em> = 0.25–0.5) that balances favorable formation energy (−59.5 kJ/mol·H₂), moderate hydrogen binding (−1.22 eV), and robust thermodynamic stability. These findings establish a quantitative framework for designing perovskite hydrides with tailored hydrogen storage properties through controlled cation substitution, specifically targeting applications where high volumetric density is a critical requirement.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115663"},"PeriodicalIF":3.0,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145974357","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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A DFT study on the antioxidant mechanism of hibiscetin against the scavenging of hydroxyl and hydroperoxyl radicals 木糖素抗氧化机制的DFT研究清除羟基和羟基自由基

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2026-03-01 Epub Date: 2026-01-11 DOI: 10.1016/j.comptc.2026.115665

C. Ragi, G.S. Gopika Krishnan, K. Muraleedharan

引用次数: 0

A theoretical study on mechanism and kinetics of o-toluidine with NH2 radicals 邻甲苯胺与NH2自由基反应机理及动力学的理论研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2026-03-01 Epub Date: 2026-01-18 DOI: 10.1016/j.comptc.2026.115686

Tien V. Pham, Anh V. Tran, Nghia T. Nguyen

{"title":"A theoretical study on mechanism and kinetics of o-toluidine with NH2 radicals","authors":"Tien V. Pham, Anh V. Tran, Nghia T. Nguyen","doi":"10.1016/j.comptc.2026.115686","DOIUrl":"10.1016/j.comptc.2026.115686","url":null,"abstract":"<div><div>The reaction between <em>o</em>-Toluidine and NH<sub>2</sub> radicals has been studied through a detailed potential energy surface analysis at the CCSD(T)//M06-2×/aug-cc-pVTZ level of theory. Both NH<sub>2</sub>-addition and H-abstraction pathways were examined, and temperature- and pressure-dependent rate coefficients were determined within 300–2000 K and 1–76,000 Torr via TST and RRKM theories. The results show that PR<sub>1</sub>(<em>o</em>-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>NH) and PR<sub>3</sub>(<em>m</em>-C<sub>6</sub>H<sub>3</sub>(CH<sub>3</sub>)NH<sub>2</sub>) dominate, with branching ratios of 27–44% and 27–30%, respectively. The overall rate constant at 760 Torr follows <em>k</em>(<em>T</em>) = 9.12 × 10<sup>−27</sup> T<sup>4.61</sup> exp.(−2.97 ± 0.41 kcal/mol/RT) cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>. This study provides valuable mechanistic and kinetic insights into the reactivity of amine-substituted aromatic compounds, offering a fundamental basis for understanding radical-induced transformations in atmospheric and combustion chemistry.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115686"},"PeriodicalIF":3.0,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023775","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}

引用次数: 0

Layer-dependent band-gap evolution and convergence in R-TiO₂(110) surfaces r- tio2（110）表面的带隙演化与收敛

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2026-03-01 Epub Date: 2026-01-15 DOI: 10.1016/j.comptc.2026.115680

Jiahui Wu , Xinyu Xie , Yunxiang He , Yutong Zhang , Caifang Han , Dandan Wang , Hongwei Li , Ruimin Wang

{"title":"Layer-dependent band-gap evolution and convergence in R-TiO₂(110) surfaces","authors":"Jiahui Wu , Xinyu Xie , Yunxiang He , Yutong Zhang , Caifang Han , Dandan Wang , Hongwei Li , Ruimin Wang","doi":"10.1016/j.comptc.2026.115680","DOIUrl":"10.1016/j.comptc.2026.115680","url":null,"abstract":"<div><div>The surface electronic structure of titanium dioxide governs its photocatalytic performance, but the depth of surface effects and the minimum reliable slab thickness remain uncertain. We systematically study rutile TiO₂(110) slabs (10–36 layers) using first-principles calculations. The local band gap evolves in a distinct “W”-shaped profile. Its minimum shifts inward with thickness and converges at the 8th atomic layer for slabs ≥30 layers, defining the surface-to-bulk transition. The valence band maximum arises from inner-layer O 2p orbitals, while the conduction band minimum is dominated by near-surface Ti 3d orbitals. An odd/even layer-number oscillation is also identified. This work establishes ≥30 layers (∼6 nm) as the critical thickness for accurately capturing surface electronic properties and ensuring bulk convergence. These results offer a quantitative model-selection benchmark and atomic-scale insight into surface evolution, aiding the design of optimized TiO₂ devices via surface engineering.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115680"},"PeriodicalIF":3.0,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023776","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}

引用次数: 0

Computational study of phosphorus-bearing molecule adsorption on amorphous silica: energetics and infrared signatures with relevance for interstellar and terrestrial chemistry 含磷分子在无定形二氧化硅上吸附的计算研究：与星际和地球化学相关的能量学和红外特征

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2026-03-01 Epub Date: 2025-12-29 DOI: 10.1016/j.comptc.2025.115652

Mireille Amandjigbeto , Etienne P. Hessou , Gaston Kpotin , Yacolé G.S. Atohoun , Ionut Tranca , Vicente Timon , Frederik Tielens

{"title":"Computational study of phosphorus-bearing molecule adsorption on amorphous silica: energetics and infrared signatures with relevance for interstellar and terrestrial chemistry","authors":"Mireille Amandjigbeto , Etienne P. Hessou , Gaston Kpotin , Yacolé G.S. Atohoun , Ionut Tranca , Vicente Timon , Frederik Tielens","doi":"10.1016/j.comptc.2025.115652","DOIUrl":"10.1016/j.comptc.2025.115652","url":null,"abstract":"<div><div>The adsorption behaviour of five phosphorus-bearing molecules (PO, PO<sub>2</sub>, POH, HPO and PH<sub>3</sub>) on amorphous silica, as a representative model not only for interstellar silicate dust grains but also for terrestrial silicate surfaces that play a role in prebiotic and geochemical processes, has been investigated to elucidate their sorption and spectroscopic characteristics. The dispersion-corrected density functional theory (DFT-D3) within the VASP framework was employed. The calculated adsorption energies are all negative, indicating that the adsorption processes are exothermic and thermodynamically favorable. Intermolecular distances and Bader charges confirm chemisorption as the dominant interaction mode, consistent with the observed energetics. Infrared (IR) spectra further demonstrate the formation of chemical bonds between the adsorbed species and the silica surface. While the spectra of PO and PO₂ exhibit similarities and overlapping vibrational features, the PO₂ spectrum can be uniquely identified by an asymmetric stretching vibration at 1253 cm<sup>−1</sup>. The POH spectrum is distinguished by a peak at 2301 cm<sup>−1</sup>, arising from the interaction of phosphorus with a silanol hydrogen. The HPO spectrum features a characteristic peak at 2075 cm<sup>−1</sup>, corresponding to the H–PO stretching vibration. Finally, PH<sub>3</sub> exhibits peaks at 2313 cm<sup>−1</sup>, assigned to the P<img>H stretching vibration.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1257 ","pages":"Article 115652"},"PeriodicalIF":3.0,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923699","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}

引用次数: 0