Computational and Theoretical Chemistry最新文献_第10页

Interpretation of the correlation energy of atoms, and its dependence with atomic number Z up to Z = 18 解释原子的相关能，以及它与原子序数Z直到Z = 18的关系

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-23 DOI: 10.1016/j.comptc.2025.115298

Julio A. Alonso , Nicolás A. Cordero

{"title":"Interpretation of the correlation energy of atoms, and its dependence with atomic number Z up to Z = 18","authors":"Julio A. Alonso , Nicolás A. Cordero","doi":"10.1016/j.comptc.2025.115298","DOIUrl":"10.1016/j.comptc.2025.115298","url":null,"abstract":"<div><div>Accurate correlation energies Ecorr of neutral atoms with atomic number Z = 1–18, calculated from a combination of experimental and theoretical information, are available in the literature. Those empirical correlation energies show a grossly linear behaviour with Z. However, in more detail Ecorr deviates from global linearity and reveals a piece-wise linear behaviour with different slopes as the different electronic shells are progressively filled. This behaviour can be explained by writing Ecorr as a sum of pairing-correlation contributions. The pairing-correlation energies have been obtained from the empirical total correlation energies of atoms. Those pairing-correlations are very weak for electrons in different main shells (K, L, M shells) and larger for electrons in the same main shell. In addition, the pairing-correlation energies depend on the angular momenta of the two electronic orbitals. Those features are due to the role of the quantum overlap between the wave functions of the electrons involved in the pairing. Pairs of electrons showing a very small orbital overlap lead to negligible pairing-correlation energies. Keeping a reasonable number of terms, the shell- and angular momentum-dependent pairing-correlation energies explain well the intricate piece-wise linear behaviour of Ecorr(Z) up to Z = 18. Also, certain approximations applied to the pairing-correlation energies permit to justify the grossly linear trend of Ecorr with Z, and the more precise faster-than-linear behaviour of Ecorr(Z).</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115298"},"PeriodicalIF":3.0,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144139477","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

Tuning NO2 selectivity in MoSe2 sensors via metal modification: Fermi-level electronic state control 通过金属修饰调整MoSe2传感器中的NO2选择性：费米能级电子状态控制

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-22 DOI: 10.1016/j.comptc.2025.115296

Chaohe Song , Lin Tao , Jie Dang , Davoud Dastan , Wensen Wang , Xueyuan Zhang , Lixiang Li , Baigang An

{"title":"Tuning NO2 selectivity in MoSe2 sensors via metal modification: Fermi-level electronic state control","authors":"Chaohe Song , Lin Tao , Jie Dang , Davoud Dastan , Wensen Wang , Xueyuan Zhang , Lixiang Li , Baigang An","doi":"10.1016/j.comptc.2025.115296","DOIUrl":"10.1016/j.comptc.2025.115296","url":null,"abstract":"<div><div>In this study, density functional theory was employed to investigate the selective adsorption of NO2 on the monolayers of MoSe2 modified by Ag and Pd. The results of the cohesive energy calculations indicate that the MoSe2 (4.38 eV) and TM-MoSe2 (4.35 eV) monolayer materials possess structural stability. The adsorption energy results demonstrate that the metal-doped/loaded structures of Ag-MoSe2 (−3.91 eV, −4.05 eV) and Pd-MoSe2 (−3.84 eV, −4.09 eV) exhibit excellent adsorption performance for NO2. By means of the d-band center theory, the energy differences caused by Ag/Pd-MoSe2 during the adsorption process were revealed. Crucially, according to the DOS analysis, when multiple gases coexist, the doped and loaded metals only produce a significant electrical response to NO2, effectively eliminating the interference from H2O and other gases. In terms of practicality, calculations of the Gibbs free energy and the Einstein diffusion equation show that the doped/loaded Ag/Pd-MoSe2 monolayers possess thermal stability (< 900 K) and a lower diffusion energy barrier (2.4 kJ mol−1). The results indicate that the material with metal doping exhibits a higher response performance to NO2 than that with metal loading, providing new ideas for the development of novel two-dimensional material-based gas sensors.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115296"},"PeriodicalIF":3.0,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144115105","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

Structural and electronic properties of neutral and anionic magnesium clusters doped with a carbon atom 掺杂碳原子的中性和阴离子镁簇的结构和电子特性

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-21 DOI: 10.1016/j.comptc.2025.115294

Zhi Zhao , Jie Zhou , Na Wang , Mingyang Gao , Yu Xie , Xiangjun Kuang , Tingting Song

{"title":"Structural and electronic properties of neutral and anionic magnesium clusters doped with a carbon atom","authors":"Zhi Zhao , Jie Zhou , Na Wang , Mingyang Gao , Yu Xie , Xiangjun Kuang , Tingting Song","doi":"10.1016/j.comptc.2025.115294","DOIUrl":"10.1016/j.comptc.2025.115294","url":null,"abstract":"<div><div>To elucidate the effect of carbon doping in magnesium cluster systems, we employ density functional theory (DFT) calculations to systematically investigate the structural evolution and electronic properties of MgnC0/− clusters (n = 2–15). The findings demonstrate that the most stable structure of MgnC0/− clusters is three-dimensional at n ≥ 3. Notably, the majority of the lowest-energy MgnC0/− configurations (n = 2–15) are not structurally consistent with those derived from substituting a single Mg atom in Mgn+1 clusters with carbon—a result that shows C doping induces structural reorganization rather than simple substitution. A comparison of the shortest Mg<img>Mg bond lengths reveals that anion incorporation promotes more stable configurations in clusters with n > 7. The reduced HOMO-LUMO gap observed in MgnC− clusters (with n > 4) compared to neutral MgnC clusters suggests that anion incorporation enhances their chemical reactivity and metallic character. For all MgnC0/− clusters, charge is transferred from the Mgn motif to the C atom. A stability analysis reveals that the C2v-symmetric Mg8C cluster exhibits robust stability. Further investigation into molecular orbitals and bonding of Mg8C demonstrates that Mg8C not only fulfills 1S21P61D42S21D6 closed-shell layer structure with 20 valence electrons but also develops strong covalent C<img>Mg and Mg<img>Mg bonds.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115294"},"PeriodicalIF":3.0,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144139478","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

Studies on the bent thoracene with low coordinated bridging units using density functional theory 基于密度泛函理论的低协调桥单位弯曲胸的研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-21 DOI: 10.1016/j.comptc.2025.115295

Sarita Yadav, Pooja, Ravinder Pawar

{"title":"Studies on the bent thoracene with low coordinated bridging units using density functional theory","authors":"Sarita Yadav, Pooja, Ravinder Pawar","doi":"10.1016/j.comptc.2025.115295","DOIUrl":"10.1016/j.comptc.2025.115295","url":null,"abstract":"<div><div>Metallocenophanes are well established as the most prominent organometallic analogs of cyclophanes. In contrast, the intriguing domain of actinocenophanes remains largely unexplored. Hence, density functional theory (DFT) calculations are employed in the present study to investigate a series of [3]thoracenophanes incorporating X-Y-X ansa moieties. These moieties feature a low-coordinated center Y (comprising C, Si, or Ge), stabilized by adjacent donor units X (NMe, O, or S). These ansa-bridged [3]thoracenophanes predominantly feature cyclooctatetraene dianion (COT2−) in an eclipsed configuration. Notably, a tilting of the COT2−rings is observed when thoracene is bridged with second-row elements, in contrast to the third-row elements. Analysis of the singlet-triplet gap (<math><mo>∆</mo><msub><mi>E</mi><mrow><mi>s</mi><mo>−</mo><mi>t</mi></mrow></msub></math>) reveals that the triplet states of all investigated carbenes possess higher energy than the corresponding singlet states. Frontier molecular orbital (FMO) analysis further demonstrates that the identity of the heteroatom (X) in the ansa moiety plays a crucial role in stabilizing the low-coordinated carbon (C) of the thoracenophane complex. Furthermore, natural bond orbital (NBO) analysis was conducted to comprehend the stabilization of the resulting carbene-based thoracenophane complexes. The results reveal that, intriguingly, no direct orbital interaction occurs between the thorium center and the ansa bridge, highlighting the primary role of the carbene-based low-coordinated ansa unit in altering the properties through geometrical modifications. This study opens a new avenue for exploring the reactivity patterns of these [3]thoracenophanes toward small-molecule activation and for extending the ansa-bridge design to other actinides for advanced catalytic applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115295"},"PeriodicalIF":3.0,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144134512","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

Density functional theory investigations of the electronic structure and magnetic properties of transition metal MII/GdIII complexes (M = Co and Cu) 过渡金属MII/GdIII配合物（M = Co和Cu）电子结构和磁性能的密度泛函理论研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-21 DOI: 10.1016/j.comptc.2025.115293

Billel Teyar , Abdelkader Ladjarafi , Abdellah Zaiter , Abdou Boucekkine

{"title":"Density functional theory investigations of the electronic structure and magnetic properties of transition metal MII/GdIII complexes (M = Co and Cu)","authors":"Billel Teyar , Abdelkader Ladjarafi , Abdellah Zaiter , Abdou Boucekkine","doi":"10.1016/j.comptc.2025.115293","DOIUrl":"10.1016/j.comptc.2025.115293","url":null,"abstract":"<div><div>A relativistic DFT study of two mixed MII and GdIII bimetallic complexes with the following general formula: LMGd(μ-O2CCH3)(O2CCH3)2 with (M = Co and Cu) and (L = 6,6′-((1E,1′E)-((2,2-Dimethylpropane1,3-diyl)bis(azanylylidene))bis(methanylylidene))bis(2-methoxyphenol) has been carried out. The computations have been conducted at the scalar relativistic ZORA/B3LYP/TZP level. First, a good agreement between the optimized geometries and the X-ray ones has been obtained. The computation of the magnetic exchange coupling constants using the Broken Symmetry approach (BS) at the same level of theory has been done. Using their fully optimized geometries we obtained the following coupling constants, indicating a ferromagnetic character for both complexes, J = +0.26 cm−1 and J = +1.49 cm−1 respectively, values close to the experimental results, namely J = +0.22 cm−1 and J = +2.6 cm−1. The electronic structures have been rationalized considering the MO diagrams, the distributions of atomic spin densities, in conjunction with Natural Population Analysis (NPA) and Multipole Derived Charge (MDC) analysis. The analysis of the spin populations indicates the localization of the seven 4f unpaired electrons of the Gd(III) ion on the metal center, whereas a significant delocalization of the 3d electrons of the M(II) ion occurs. The driving role of the Cu-O-Gd angle on the magnetic behavior has been investigated. It is found that the actual angle value i.e. 103.44° insures the highest values of the bond orders within the magnetic core, the core oxygen spin populations reaching their maximum value, favoring the superexchange mechanism; concomitantly, the highest value of the coupling constant is obtained.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115293"},"PeriodicalIF":3.0,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144139476","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

Insights into the turn-on mechanism of SNN fluorescent probe for Al3+ and Zn2+ detection SNN荧光探针检测Al3+和Zn2+的开启机制研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-20 DOI: 10.1016/j.comptc.2025.115291

Siqi Wang , Jieyi Wang , Jiayi Cui , Wenbo Li , Yusheng Weng , Hongjing Liang , Hui Li , Guangyong Jin

{"title":"Insights into the turn-on mechanism of SNN fluorescent probe for Al3+ and Zn2+ detection","authors":"Siqi Wang , Jieyi Wang , Jiayi Cui , Wenbo Li , Yusheng Weng , Hongjing Liang , Hui Li , Guangyong Jin","doi":"10.1016/j.comptc.2025.115291","DOIUrl":"10.1016/j.comptc.2025.115291","url":null,"abstract":"<div><div>The rapid detection of metal ions in organisms and the environment is crucial. A comprehensive understanding of sensing mechanisms is essential for developing efficient probes. We systematically investigate the dynamical process and luminescence properties of the SNN probe and its complexes using the time-dependent density functional theory (TD-DFT) methods. By analyzing the potential energy surface and Born-Oppenheimer molecular dynamics simulations, we found that the twisted intramolecular charge transfer (TICT) process in the excited state of the SNN molecule inhibits the excited-state intramolecular proton transfer (ESIPT) process, leading to fluorescence quenching. However, upon binding with Al3+ or Zn2+, the molecular structural torsion is restricted, significantly enhancing fluorescence emission. Consequently, the complexes SNN-Zn2+ and SNN-Al3+ emit bright fluorescence. The computational results help elucidate how metal ions activate the luminescent properties of the probe and its response mechanism, providing valuable theoretical guidance and reference for the design and development of novel fluorescent probes.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115291"},"PeriodicalIF":3.0,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144115016","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

Theoretical exploration of the structural evolution and electronic properties of LiAln−/0 (n = 3–20) clusters LiAln−/0 （n = 3-20）团簇结构演化和电子性质的理论探索

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-20 DOI: 10.1016/j.comptc.2025.115292

Kai Wang , Rui Chen , Yabing Du , Chaoyong Wang , Renqi Zhang , Luyan Xu , Huanjian Xie

{"title":"Theoretical exploration of the structural evolution and electronic properties of LiAln−/0 (n = 3–20) clusters","authors":"Kai Wang , Rui Chen , Yabing Du , Chaoyong Wang , Renqi Zhang , Luyan Xu , Huanjian Xie","doi":"10.1016/j.comptc.2025.115292","DOIUrl":"10.1016/j.comptc.2025.115292","url":null,"abstract":"<div><div>We performed a theoretical study on the structures and electronic properties of LiAln−/0 (n = 3–20) clusters using a hybrid global optimization algorithm and density functional theory (DFT). The ground-state structures of LiAln− (n = 3–15) anions were confirmed based on good matching results between simulated and experimental photoelectron spectra. These LiAln−/0 (n = 3–20) clusters prefer to adopt Aln clusters as the structural motifs with the Li atom absorbed on the surface. The neutral LiAln clusters maintain identical structural configurations with their anionic counterparts for most sizes, with the notable exception for sizes n = 17–20. In LiAln−/0 clusters, Li always contributes electrons to the Aln. Doping Li atom has significant effects on the electronic properties of Aln clusters. Neutral AMAl13 (AM = Li Na, K, Rb, Cs) and anionic Al13− are confirmed as superatoms with the electronic configuration of (1S)2(1P)6(1D)10(2S)2(1F)14(2P)6, as same as that of the gallium-based counterparts.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115292"},"PeriodicalIF":3.0,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144124566","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

Z-scheme van der Waals heterostructure of BC6N/Blue-Phosphorene as a promising visible-light photocatalyst BC6N/蓝磷烯的z型范德华异质结构作为一种很有前途的可见光催化剂

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-19 DOI: 10.1016/j.comptc.2025.115276

Sreejani Karmakar, Sudipta Dutta

{"title":"Z-scheme van der Waals heterostructure of BC6N/Blue-Phosphorene as a promising visible-light photocatalyst","authors":"Sreejani Karmakar, Sudipta Dutta","doi":"10.1016/j.comptc.2025.115276","DOIUrl":"10.1016/j.comptc.2025.115276","url":null,"abstract":"<div><div>Two-dimensional van der Waals heterostructures have had a great impact on designing efficient photocatalysts. Through first-principle calculations, we explore the prospect of BC6N/blue-phosphorene heterostructure in metal-free photocatalysis. To investigate the photocatalytic ability and the underlying mechanism, we calculate its optoelectronic, thermodynamic, and charge migration properties. This indirect band-gap semiconductor has a gap of 1.6 eV and provides suitably aligned band-edges to simultaneously perform photocatalytic oxidation and reduction. Moreover, the internal electric field makes the photogenerated electrons follow the Z-scheme pathway, which ensures efficient electron–hole separation without compromising the thermodynamic drive for the catalytic reactions. Additionally, the red-shifted absorption spectra of the heterostructure promote high photon harvest in the visible range upon solar illumination. The synergy of improved charge separation and increased number of harvested photons would drastically boost the photocatalytic performance. These results establish BC6N/blue-phosphorene as potential visible-light-driven metal-free photocatalysts that address diverse environmental challenges.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115276"},"PeriodicalIF":3.0,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144167778","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

Cu or Rh-doped InSe monolayers for acid rain gas detection and capture: Insights from first-principles calculations 用于酸雨气体检测和捕获的铜或铑掺杂铟硒单层：来自第一性原理计算的见解

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-16 DOI: 10.1016/j.comptc.2025.115281

Xiao-Qian Lin , Xin Zhang , Ming-Ling Sun , Peng-Bin Pan , Yuan-Gen Yao

{"title":"Cu or Rh-doped InSe monolayers for acid rain gas detection and capture: Insights from first-principles calculations","authors":"Xiao-Qian Lin , Xin Zhang , Ming-Ling Sun , Peng-Bin Pan , Yuan-Gen Yao","doi":"10.1016/j.comptc.2025.115281","DOIUrl":"10.1016/j.comptc.2025.115281","url":null,"abstract":"<div><div>Acid rain gases, such as nitric oxide (NO), nitrogen dioxide (NO2), sulfur dioxide (SO2), and sulfur trioxide (SO3), pose serious environmental and health risks, highlighting the urgent need for efficient materials for their detection and capture. In this study, the gas sensing and adsorption properties of Cu- or Rh-doped InSe monolayers were systematically investigated using first-principles calculations. The results demonstrate that Cu doping significantly enhances the gas sensing sensitivity of InSe, particularly toward NO2, SO2, and SO3, and maintains high sensitivity even at elevated temperatures. However, the prolonged recovery times of Cu-doped InSe limit its potential for real-time sensing, making it more suitable for gas scavenging applications. In contrast, Rh doping results in much stronger gas adsorption and ultra-long recovery times, rendering Rh-doped InSe a promising candidate for long-term gas capture and storage. Pristine InSe, with its weak interactions and low sensitivity, is unsuitable for gas sensing or scavenging. Overall, Cu-doped InSe is promising for gas detection, while Rh-doped InSe is better suited for long-term pollutant removal. These findings provide valuable insights for the design of multifunctional two-dimensional materials for environmental monitoring and pollutant control.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115281"},"PeriodicalIF":3.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144089544","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

Regulating fluorescent properties and ESIPT behavior of novel scaffold-based fluorescent molecule by different substituents: A TD-DFT study 不同取代基对新型支架荧光分子荧光特性和ESIPT行为的调控：TD-DFT研究

IF 3 3区化学

Computational and Theoretical Chemistry Pub Date : 2025-05-15 DOI: 10.1016/j.comptc.2025.115278

Feiyang Yin, Hua Fang

{"title":"Regulating fluorescent properties and ESIPT behavior of novel scaffold-based fluorescent molecule by different substituents: A TD-DFT study","authors":"Feiyang Yin, Hua Fang","doi":"10.1016/j.comptc.2025.115278","DOIUrl":"10.1016/j.comptc.2025.115278","url":null,"abstract":"<div><div>Recently, a new fluorophore 5-bis(benzo[d]thiazol-2-yl)phenol (BTP) is synthesized experimentally, and BTP-based probe can successfully recognize cysteine (Cys) quickly and sensitively (Spectrochim. Acta Part A 217 (2019) 1–7). Via introducing the –CN and/or –N(CH3)2 groups into BTP, three novel compounds (BTP-1, BTP-2 and BTP-3) are designed to investigate the substituent effects on the photophysical properties and excited state intramolecular proton transfer (ESIPT) process of BTP. The structural parameters, infrared (IR) vibrational spectra, electron densities and reduced density gradient (RDG) isosurfaces obtained by density functional theory (DFT) and time-dependent DFT (TD-DFT) methods have indicated that the intramolecular hydrogen bonds (IHBs) of BTP derivatives became stronger in the excited (S1) state. The introduction of substituent leads to a bathochromic-shift of the absorption and fluorescence peaks. Meanwhile, from the potential energy curves, it can be found that the introduction of two –CN groups can effectively decrease the ESIPT energy barrier of BTP, while the coexistence of –CN and –N(CH3)2 hinder the ESIPT process.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1250 ","pages":"Article 115278"},"PeriodicalIF":3.0,"publicationDate":"2025-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144070900","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