Computational and Theoretical Chemistry最新文献

{"title":"A theoretical study of the effect of end-group and center backbone modifications on the optoelectronic properties of Y6-based asymmetric LL3 non-fullerene","authors":"Liu Yang,&nbsp;Yunjie Xiang,&nbsp;Shaohui Zheng","doi":"10.1016/j.comptc.2025.115208","DOIUrl":"10.1016/j.comptc.2025.115208","url":null,"abstract":"<div><div>Y6-based non-fullerene acceptor (NFA) has garnered significant attention because of its unique A-DA'D-A molecular structure. However, the impact of asymmetric modification—a key strategy to enhance NFAs—on their photovoltaic properties is still not well understood. In this study, we optimized the high-performance asymmetric LL3, a Y6-based NFA characterized by its distinctive 3D end-group structure, by employing end-group and skeleton modification techniques. We designed six new asymmetric NFA candidates by expanding thiophene rings within the skeleton's core, incorporating π-bridges, and substituting chlorinated benzene rings or 3D segments at the end-groups with thiophene. Using density functional theory (DFT) and time-dependent DFT (TD-DFT), we calculated various molecular properties of these NFAs, such as molecular planarity, dipole moments, frontier molecular orbitals, electrostatic potential (ESP), electron-hole distributions, UV–Visible absorption spectra, singlet-triplet energy difference (ΔE_ST), exciton binding energy (E_b), and the open circuit voltages of organic solar cells based on these NFAs. Our results show that five of the new NFAs outperform the prototype LL3, with LL3-T-L standing out due to its red-shifted absorption peak, highest light absorption intensity, lower ΔE_ST and E_b, and enhanced ESP, indicating its potential as a high-performance NFA. These findings provide theoretical guidance for future experimental synthesis and device optimization.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115208"},"PeriodicalIF":3.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143715743","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":"Modeling electronic structure and charge transport properties of Tetrathienopyrrole-based hole-transporting materials: A DFT approach for enhanced photovoltaic efficiency towards efficient perovskite solar cells","authors":"Rida Fatima ,&nbsp;Nabeel Shahzad ,&nbsp;Mahwish Iqbal ,&nbsp;Tahreem Fatima ,&nbsp;Shaimaa A.M. Abdelmohsen ,&nbsp;Javed Iqbal","doi":"10.1016/j.comptc.2025.115204","DOIUrl":"10.1016/j.comptc.2025.115204","url":null,"abstract":"<div><div>This quantum mechanical approach paved the way for fabricating highly stable hole-transporting materials for photovoltaic cells. This scheme involved the integration of acceptor terminal units through a thiophene spacer to the versatile symmetrical tetrathienopyrrole core connected to dimethoxytriphenylamine helix units, resulting in a series of six novel HTMs (DTT-1 to DTT-6). Comprehensive analysis of the energetics of energy levels (HOMO/LUMO), solvation energy, density of states (DOS), and stability of proposed HTMs were evaluated by systematically performing the quantum computation via (DFT) and (TD-DFT). The results revealed that fabricated HTMs (DTT-1 to DTT-6 unveiled stabilized HOMO levels approaching the edge with suitable HTM/perovskite energy level alignment, proposing exceptional charge extraction and high open circuit voltage. Photophysical analysis indicated that our fabricated HTMs revealed larger Stokes shift values (75 nm −150 nm) and transparency in the visible region, allowing full utilization of sunlight for the perovskite layer for photocurrent generation and enhanced spectral selectivity. The proposed HTMs showed smaller RE values ranging from 0.106 eV to 0.23 eV and greater transfer integral, signifying ultrafast hole mobility. Moreover, comparatively higher dipole moments (2.81 D-11.07 D) and higher negative solvation energies (−18.62 kcal/mol to −21.86 kcal/mol) suggested improved solubility and film-forming attributes. Hence, this study provides crucial insights into the deliberate and effective design of high-performance HTMs.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115204"},"PeriodicalIF":3.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143716147","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":"Rational design and DFT-based study of non-fullerene acceptors for high-performance organic solar cells: End-cap and Core modifications for enhanced charge transfer","authors":"Adeel Mubarik,&nbsp;Faiza Shafiq,&nbsp;Xue-Hai Ju","doi":"10.1016/j.comptc.2025.115209","DOIUrl":"10.1016/j.comptc.2025.115209","url":null,"abstract":"<div><div>In this article, we reported the 64 newly designed non-fullerene acceptors (NFAs) using density functional theory (DFT) approaches combined with both central core and end-cap modification. We screened out five promising molecules among 64 molecules using four specific criteria and their structural as well as optoelectronic attributes were calculated. Using DFT techniques, we thoroughly examined the optical, electrical, and excited state characteristics such as energy gap, maximum absorption, excitation energy (<em>E</em>_<em>x</em>), and oscillator strength to evaluate the effects of various end-cap groups on different core architectures. Furthermore, we paired the most promising NFAs with the P3HT polymer donor to generate donor-acceptor interfaces, and we examined the open circuit voltage (<em>V</em>_<em>oc</em>) and rate of charge transfer (CT) at these interfaces. The conclusions offer insightful advice and useful design guidelines for high-performance NFAs that have the potential to greatly increase solar devices' efficiency.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115209"},"PeriodicalIF":3.0,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726216","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":"First-principles study on single-layer electronic structure of Fe-doped MoS2 and the reduction of NO on the doped surface","authors":"Xiangzhen Xiao ,&nbsp;Yinli Cao ,&nbsp;Linfeng Hu","doi":"10.1016/j.comptc.2025.115172","DOIUrl":"10.1016/j.comptc.2025.115172","url":null,"abstract":"<div><div>Electrocatalytic reduction represents an effective approach for the conversion of the harmful gas nitric oxide (NO) into ammonia (NH₃), a vital chemical precursor in industrial production. However, the large-scale practical application of NO electrocatalytic reduction remains a significant challenge, particularly in the identification of efficient, low-cost, and stable catalysts. In this study, we investigate the electronic structure, magnetic properties, and stability of the Fe-MoS₂ doping system using first-principles calculations. We explore the activation mechanism of NO molecules by Fe-MoS₂ and assess its potential as an electrocatalyst for NO reduction by examining the electronic structure of the adsorbed states. Our results show that Fe doping effectively modulates the electronic structure of MoS₂, significantly enhancing its capacity to adsorb NO compared to pristine molybdenum disulfide surfaces. Analysis of charge transfer and electronic properties during NO adsorption reveals a charge transfer of 0.32e between the substrate and the adsorbed NO molecule. Furthermore, the 2p<span><math><msub><mrow></mrow><mrow><mi>y</mi></mrow></msub></math></span> and 2p<span><math><msub><mrow></mrow><mrow><mi>x</mi></mrow></msub></math></span> orbitals of the nitrogen atom exhibit partial overlap with the 3d<span><math><msub><mrow></mrow><mrow><mi>xy</mi></mrow></msub></math></span>, 3d<span><math><msub><mrow></mrow><mrow><mi>yz</mi></mrow></msub></math></span>, and 3d<span><math><msub><mrow></mrow><mrow><mi>xz</mi></mrow></msub></math></span> orbitals of the Fe atom near the Fermi level, indicating strong interactions that facilitate NO activation. The hydrogenation process of NO to ammonia was further investigated using two different approaches. The results demonstrated the exceptional electrocatalytic reduction activity of Fe-doped S vacancy towards NO. This study not only provides a concise depiction of the Fe-MoS₂ electrocatalyst but also verifies the feasibility of utilizing Fe-MoS₂ for the electrocatalytic synthesis of ammonia from NO.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115172"},"PeriodicalIF":3.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143705491","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 study of catalytic performance of X-γ-Graphyne as cathodes for lithium-air batteries","authors":"Armando Vera-Garcia ,&nbsp;J.H. Pacheco-Sanchez ,&nbsp;Frank J. Isidro-Ortega ,&nbsp;Abraham González-Ruíz ,&nbsp;J.S. Arellano","doi":"10.1016/j.comptc.2025.115197","DOIUrl":"10.1016/j.comptc.2025.115197","url":null,"abstract":"<div><div>Lithium-air batteries (Li<img>O₂) are considered one of the most promising energy storage and conversion device candidates for future mobility applications, such as electric vehicles, due to their ultrahigh theoretical energy density (up to ∼3600 Wh kg^‐1). The main goal in this work is to study an electrochemical catalytic model for a cathode in Li<img>O₂ batteries to simulate the OER during the discharging process. Density Functional Theory (DFT) calculations were performed to investigate γ-Graphyne and N-γ-Graphyne (N-Doped γ-Graphyne) as the potential cathode catalyst for Li<img>O₂ batteries. γ-Graphyne and N-γ-Graphyne surfaces exhibit high stability according to calculations, the pristine surface exhibits a slight improvement in the formation energy of Li_xO₂, moreover, the N-Doped surface can reduce the significant formation energy of Li_xO₂ in the OER. Calculations explain the catalytic mechanism and identify the active sites to perform N-doping on pristine γ-Graphyne. This study demonstrates a feasible approach to achieve designed γ-Graphyne and N-γ-Graphyne as cathode catalysts for Li air batteries, which is promising for cost reduction in mass production of Li-air batteries.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115197"},"PeriodicalIF":3.0,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726219","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 calculations of thermal functions of diatomic molecules using shifted Deng-Fan potential","authors":"Ahmad Ghanbari","doi":"10.1016/j.comptc.2025.115186","DOIUrl":"10.1016/j.comptc.2025.115186","url":null,"abstract":"<div><div>We have theoretically investigated the thermodynamic properties of diatomic molecules using shifted Deng-Fan potential. To this end, we have solved the Schrödinger eq. (SE) with the oscillator potential applying the Nikiforov-Uvarov method and have obtained energy eigenvalues. Using calculated eigenvalues, we have determined partition function and thermodynamic properties of diatomic molecules such as H₂, HCl and LiH. We have obtained the properties like mean energy, specific heat in constant volume, entropy and free energy. Also, we have calculated specific heat in constant pressure, enthalpy and Gibbs free energy of the molecules and compared our calculated data with experimental data. Our results show that there is a good agreement between them. We have determined average deviations of our results and experimental data.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115186"},"PeriodicalIF":3.0,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734517","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 investigation on the reaction kinetics of H with furfural","authors":"Qiongxuan Zhu ,&nbsp;Lili Xing ,&nbsp;Liuchao Lian ,&nbsp;Jing Zhu ,&nbsp;Xuetao Wang","doi":"10.1016/j.comptc.2025.115190","DOIUrl":"10.1016/j.comptc.2025.115190","url":null,"abstract":"<div><div>The reaction between furfural and H plays a crucial role in its thermal decomposition, but its specific kinetic data are not yet available. We used a high-level quantum chemistry method to model the potential energy surface of the furfural + H system. According to the potential energy surface, H-addition to the C_ε site has the highest energy barrier, while H-addition to the C_δ position has the lowest energy barrier. In the low-temperature range of 298-600 K, H-abstraction is faster than preliminary H-addition reaction. However, the H-addition reaction dominates when T&gt;600K. Subsequent reaction pathways of the formed intermediates were also analyzed. The temperature and pressure dependence of rate constants were studied and discussed. This study reveals distinct behaviors in the rate constants for intermediates and bimolecular products across different temperature ranges. These findings could aid in developing more accurate kinetic models.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115190"},"PeriodicalIF":3.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143715742","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":"Isomorphic graphene-like building unit","authors":"Fernando Alvarez-Ramírez ,&nbsp;Ariel A. Valladares","doi":"10.1016/j.comptc.2025.115195","DOIUrl":"10.1016/j.comptc.2025.115195","url":null,"abstract":"<div><div>A novel structural unit is proposed for constructing crystalline materials and molecular systems by mimicking the morphologies of carbon in its sp² allotropic forms. The new family of layered graphene-like crystals in 2D lattices exhibit crown ether-like cycles. The proposed structures are not limited to a single chemical element, carbon, and have the potential to modulate electronic properties based on their composition. Nine combinations of atomic elements of the structural unit are presented, which give rise to structures whose electronic gaps can vary from zero to 2.597 eV for a B-N-S-Si combination of the basic unit. Depending on the atomic composition, this structural unit may give rise to unstable or stable structures. The elastic constant analysis shows that three of the proposed structures are mechanically stable, while only the N-C-O-Ni configuration is both mechanically and dynamically stable, which is confirmed by the absence of negative frequencies in the dispersion calculations.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115195"},"PeriodicalIF":3.0,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682226","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":"What drives enhanced chloride recognition of squaramide-based receptors over urea and thiourea? A computational exploration in the gas-phase and various solvents","authors":"Yasin Gholiee","doi":"10.1016/j.comptc.2025.115191","DOIUrl":"10.1016/j.comptc.2025.115191","url":null,"abstract":"<div><div>Significant progress in anion recognition has been achieved through the development of synthetic receptors. Urea-, thiourea-, and squaramide-based molecules, known for hydrogen-bonding capabilities, have gained prominence in supramolecular chemistry. The superior anion recognition of squaramide-based receptors, compared to urea- and thiourea-based ones, is repeatedly attributed to the crucial involvement of C<img>H fragments. This study computationally investigates chloride recognition by nine symmetric urea-, thiourea-, and squaramide-based receptors, focusing on solvent effects, interactions, and intrinsic affinity. The findings suggest that while C<img>H fragments aid anion recognition in squaramide-based receptors, the absence of steric repulsion and the presence of attractive forces between amide NH groups in squaramide, unlike in urea and thiourea receptors, significantly enhances anion-binding ability. Although solvation energy becomes less favorable from urea to squaramide, negative gas-phase Gibbs free energy drives complex formation. The accuracy of computational results is validated by excellent correlation between experimental and calculated formation constants.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115191"},"PeriodicalIF":3.0,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682225","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":"Examining the power of BiXO3 (X = Cr, Cu) oxide-perovskites: A first-principles study for next-generation solar cells","authors":"Hadia Khalil ,&nbsp;Misbah Tabassum ,&nbsp;Jalil Ur Rehman ,&nbsp;Syed Mansoor Ali ,&nbsp;Rajeh Alotaibi","doi":"10.1016/j.comptc.2025.115194","DOIUrl":"10.1016/j.comptc.2025.115194","url":null,"abstract":"<div><div>The current study investigates the structural, electronic, optical, and mechanical aspects of Bi-based oxide-perovskites BiXO₃ (X = Cr, Cu) while using first-principles simulations. BiCrO₃ and BiCuO₃ have lattice parameters of 3.85 and 3.87 Å, respectively. Both the materials have semiconducting properties with a direct band gap as indicated by the band structure and density of states. The computed energy band gap for BiCrO₃ and BiCuO₃ is found 1.68 and 1.36 eV, respectively. To describe how light interacts with the material, the optical characteristics of both materials are examined for photon energies between 0 and 12 eV. Based on their mechanical properties, it is found that both materials are mechanically stable, hard, and incompressible. According to Cauchy pressure and Pugh's ratio, both the compounds show a ductile behavior. The overall investigation shows that both materials are appropriate for next generation solar cells.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115194"},"PeriodicalIF":3.0,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143682227","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}