Chemical Physics最新文献

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Theoretical study of the photovoltaic properties of dye-sensitized solar cells with novel D-A-π-A-type benzothiazole molecules as auxiliary acceptors

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-12-02 DOI: 10.1016/j.chemphys.2024.112562

Hongxv Shi , Yue Liang , Baoming Hou , Yuheng Li , Meiqi Liu , Yuyu Pan , Bing Yang

The design and synthesis of low-cost-efficient sensitizer dyes is the most important approach to extend the application of dye-sensitized solar cells (DSSCs). Based on density functional theory (DFT) and time-dependent DFT (TD-DFT) approaches, a series of D-A-π-A-type dye molecules with different auxiliary acceptors were designed. The structures, frontier molecular orbital (FMO), absorption spectra (UV) are investigated theoretically. Key parameters related to short-circuit current density and open-circuit voltage, such as light-harvesting efficiency (LHE), the reorganization energies (λ), the electronic injection-free energy (ΔG_inject), and the regeneration driving forces(ΔGreg)., are calculated individually. In addition, intramolecular charge transfer (ICT) properties such as charge transfer distance (D_CT) and dipole moment change (μ_CT) were investigated. Compared with other dyes, A-7 and A-9 dyes show outstanding performance. The purpose of our study is expected to provide a promising way to design possible candidate sensitizers for DSSC.

{"title":"Theoretical study of the photovoltaic properties of dye-sensitized solar cells with novel D-A-π-A-type benzothiazole molecules as auxiliary acceptors","authors":"Hongxv Shi , Yue Liang , Baoming Hou , Yuheng Li , Meiqi Liu , Yuyu Pan , Bing Yang","doi":"10.1016/j.chemphys.2024.112562","DOIUrl":"10.1016/j.chemphys.2024.112562","url":null,"abstract":"<div><div>The design and synthesis of low-cost-efficient sensitizer dyes is the most important approach to extend the application of dye-sensitized solar cells (DSSCs). Based on density functional theory (DFT) and time-dependent DFT (TD-DFT) approaches, a series of D-A-π-A-type dye molecules with different auxiliary acceptors were designed. The structures, frontier molecular orbital (FMO), absorption spectra (UV) are investigated theoretically. Key parameters related to short-circuit current density and open-circuit voltage, such as light-harvesting efficiency (LHE), the reorganization energies (λ), the electronic injection-free energy (ΔG<sub>inject</sub>), and the regeneration driving forces(ΔGreg)., are calculated individually. In addition, intramolecular charge transfer (ICT) properties such as charge transfer distance (D<sub>CT</sub>) and dipole moment change (μ<sub>CT</sub>) were investigated. Compared with other dyes, A-7 and A-9 dyes show outstanding performance. The purpose of our study is expected to provide a promising way to design possible candidate sensitizers for DSSC.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112562"},"PeriodicalIF":2.0,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164755","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

Can different counter ions and their concentration modify the structural characteristics of aqueous solutions of uranyl ions? Atomistic insights from molecular dynamics simulations

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-11-30 DOI: 10.1016/j.chemphys.2024.112547

Amrit Pal Singh , Manish Chopra , Niharendu Choudhury

Extensive atomistic molecular dynamics simulation results suggest that probability of counter ion occupying first solvation shell of uranyl ion depends both on its nature and concentration. In general, uranyl-counter ion complexes with pentagonal bi-pyramidal structure with five ligands in the equatorial plane of the linear UO₂²⁺ ion are observed. In case of nitrate ion, pure aqua complexes at lower concentrations and mixed mono-nitro aqua complexes are observed at higher concentrations, whereas in case of sulphate and carbonate ions, no pure aqua complexes are observed. The NO₃⁻ and SO₄²⁻ ions act as unidentate, but CO₃²⁻ acts both as uni- and bi-dentate ligand. In addition, polynuclear uranium complexes with bridging SO₄²⁻ and CO₃²⁻ ligands are observed. Relative strength of binding of counter ions with uranyl ion from PMF calculations follows the order CO₃²⁻ > SO₄²⁻ > NO₃⁻ with the contact pair free energies of about −29.0, −14.0 and −1.1 kcal/mol respectively.

{"title":"Can different counter ions and their concentration modify the structural characteristics of aqueous solutions of uranyl ions? Atomistic insights from molecular dynamics simulations","authors":"Amrit Pal Singh , Manish Chopra , Niharendu Choudhury","doi":"10.1016/j.chemphys.2024.112547","DOIUrl":"10.1016/j.chemphys.2024.112547","url":null,"abstract":"<div><div>Extensive atomistic molecular dynamics simulation results suggest that probability of counter ion occupying first solvation shell of uranyl ion depends both on its nature and concentration. In general, uranyl-counter ion complexes with pentagonal bi-pyramidal structure with five ligands in the equatorial plane of the linear UO<sub>2</sub><sup>2+</sup> ion are observed. In case of nitrate ion, pure aqua complexes at lower concentrations and mixed mono-nitro aqua complexes are observed at higher concentrations, whereas in case of sulphate and carbonate ions, no pure aqua complexes are observed. The NO<sub>3</sub><sup>−</sup> and SO<sub>4</sub><sup>2−</sup> ions act as unidentate, but CO<sub>3</sub><sup>2−</sup> acts both as uni- and bi-dentate ligand. In addition, polynuclear uranium complexes with bridging SO<sub>4</sub><sup>2−</sup> and CO<sub>3</sub><sup>2−</sup> ligands are observed. Relative strength of binding of counter ions with uranyl ion from PMF calculations follows the order CO<sub>3</sub><sup>2−</sup> > SO<sub>4</sub><sup>2−</sup> > NO<sub>3</sub><sup>−</sup> with the contact pair free energies of about −29.0, −14.0 and −1.1 kcal/mol respectively.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112547"},"PeriodicalIF":2.0,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164749","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

Investigation of gas-sensitive properties of N-confused porphyrin-like graphene composites: A viewpoint of first principle

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-11-30 DOI: 10.1016/j.chemphys.2024.112546

Yuxiu Wang , Yuxuan Zhan , Zhong Xie , Cuicui Sun , Chunhua Yang

The adsorptions of H₂S and HF molecules on N-confused porphyrin-like graphene composites G-CoN_xC_4-x (x = 2, 3, and 4) are investigated by first-principles calculations. Herein, the effective physisorption between G-CoN_xC_4-x substrates and H₂S/HF toxic gases is revealed by no significant charge transfer and large adsorption spacing. Meanwhile, the exothermic adsorption effect and the thermodynamic stability of G-CoN_xC_4-x substrate are explained by the negative adsorption energies and ab initio molecular dynamics, respectively. Evidently, the G-CoN₄ shows a remarkable enhancement in the HF sensing performance while G-CoN₃C₁ and G-CoN₂C₂ systems act as sharp responsive adsorbing H₂S samples, which is confirmed by the demonstrable changes in electronic and magnetic properties, as well as reasonable short recovery time. Our comprehensive work suggests that fabricating N-confounding is an effective strategy for engineering porphyrin-like graphene-based gas sensitivity features and developing on-demand sensor.

{"title":"Investigation of gas-sensitive properties of N-confused porphyrin-like graphene composites: A viewpoint of first principle","authors":"Yuxiu Wang , Yuxuan Zhan , Zhong Xie , Cuicui Sun , Chunhua Yang","doi":"10.1016/j.chemphys.2024.112546","DOIUrl":"10.1016/j.chemphys.2024.112546","url":null,"abstract":"<div><div>The adsorptions of H<sub>2</sub>S and HF molecules on <em>N</em>-confused porphyrin-like graphene composites G-CoN<sub>x</sub>C<sub>4-x</sub> (x = 2, 3, and 4) are investigated by first-principles calculations. Herein, the effective physisorption between G-CoN<sub>x</sub>C<sub>4-x</sub> substrates and H<sub>2</sub>S/HF toxic gases is revealed by no significant charge transfer and large adsorption spacing. Meanwhile, the exothermic adsorption effect and the thermodynamic stability of G-CoN<sub>x</sub>C<sub>4-x</sub> substrate are explained by the negative adsorption energies and ab initio molecular dynamics, respectively. Evidently, the G-CoN<sub>4</sub> shows a remarkable enhancement in the HF sensing performance while G-CoN<sub>3</sub>C<sub>1</sub> and G-CoN<sub>2</sub>C<sub>2</sub> systems act as sharp responsive adsorbing H<sub>2</sub>S samples, which is confirmed by the demonstrable changes in electronic and magnetic properties, as well as reasonable short recovery time. Our comprehensive work suggests that fabricating <em>N</em>-confounding is an effective strategy for engineering porphyrin-like graphene-based gas sensitivity features and developing on-demand sensor.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112546"},"PeriodicalIF":2.0,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164757","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

Nitrogen and boron coordinating atoms adjust single-atom catalyst anchored on divacancy defect graphene for highly efficient electrochemical oxygen reduction

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-11-29 DOI: 10.1016/j.chemphys.2024.112540

Hsin-Tsung Chen , Yu-Ting Chiou , Tzu-Hui Chen , Hui-Lung Chen

In this study, spin-polarized density functional theory (DFT) calculations were utilized to explore the oxygen reduction reaction (ORR) on a transition metal anchored to divacancy graphene (TM@dv-graphene). Our findings demonstrate that divacancy graphene serves as an effective substrate for stabilizing single transition metals, thereby facilitating the ORR. We elucidate the mechanisms of ORR by examining the adsorption of O₂, OOH, OH, 2OH, and O intermediates, and identifying two competing ORR pathways: the O* and 2OH* mechanisms. Most TM@dv-graphene catalysts predominantly favor the O* mechanism, with Rh and Ir being notable exceptions that preferentially follow the 2OH* mechanism. Moreover, catalysts co-coordinated with B and N atoms significantly enhance the adsorption of key intermediates, thereby improving ORR activity Specifically, the Co-N₄, Co-N₂B₂, Pd-N₂B₂, and Pt-N₂B₂ catalysts demonstrate promising ORR activity with lower overpotentials of 0.47, 0.46, 0.58, and 0.46 V, respectively. This work establishes a foundational framework for comprehending the electrochemical mechanisms of ORR, thus facilitating the design of highly efficient single-atom electrocatalysts.

{"title":"Nitrogen and boron coordinating atoms adjust single-atom catalyst anchored on divacancy defect graphene for highly efficient electrochemical oxygen reduction","authors":"Hsin-Tsung Chen , Yu-Ting Chiou , Tzu-Hui Chen , Hui-Lung Chen","doi":"10.1016/j.chemphys.2024.112540","DOIUrl":"10.1016/j.chemphys.2024.112540","url":null,"abstract":"<div><div>In this study, spin-polarized density functional theory (DFT) calculations were utilized to explore the oxygen reduction reaction (ORR) on a transition metal anchored to divacancy graphene (TM@dv-graphene). Our findings demonstrate that divacancy graphene serves as an effective substrate for stabilizing single transition metals, thereby facilitating the ORR. We elucidate the mechanisms of ORR by examining the adsorption of O<sub>2</sub>, OOH, OH, 2OH, and O intermediates, and identifying two competing ORR pathways: the O* and 2OH* mechanisms. Most TM@dv-graphene catalysts predominantly favor the O* mechanism, with Rh and Ir being notable exceptions that preferentially follow the 2OH* mechanism. Moreover, catalysts co-coordinated with B and N atoms significantly enhance the adsorption of key intermediates, thereby improving ORR activity Specifically, the Co-N<sub>4</sub>, Co-N<sub>2</sub>B<sub>2</sub>, Pd-N<sub>2</sub>B<sub>2</sub>, and Pt-N<sub>2</sub>B<sub>2</sub> catalysts demonstrate promising ORR activity with lower overpotentials of 0.47, 0.46, 0.58, and 0.46 V, respectively. This work establishes a foundational framework for comprehending the electrochemical mechanisms of ORR, thus facilitating the design of highly efficient single-atom electrocatalysts.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112540"},"PeriodicalIF":2.0,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164118","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 isomorphic dynamic properties of biomolecular matters and glass-forming materials

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-11-28 DOI: 10.1016/j.chemphys.2024.112543

Simone Capaccioli , K.L. Ngai , Alessandro Paciaroni

Glass formation is commonly found in many different kinds of materials and systems. The conventional dynamic and thermodynamic properties considered are usually associated with the structural relaxation and the transport coefficient such as viscosity. Our studies of widely different classes of glass-forming materials over several decades have led to the discovery of processes faster than the structural relaxation are strongly connected to and inseparable from the structural relaxation in dynamic and thermodynamic properties. These faster processes include the caged molecular dynamics, and a special kind of secondary relaxation with the primitive relaxation of the Coupling Model as its precursor. Overwhelming evidences from experiments and simulations supporting this universal finding can be found in the review entitled “Universal Properties of Relaxation and Diffusion in Complex Materials: Originating from Fundamental Physics with Rich Applications“, published in Prog. Mater. Sci. 2023, 139, 101130. Consequently any theory of glass transition is neither complete nor fundamental if these important faster processes have not been considered. In this paper we examine the dynamics and thermodynamic properties of dry, hydrated, and solvated proteins and biomolecules to find the presence of the faster processes and verify their strong connections to the structural relaxation. Thus the dynamics and thermodynamics of the processes in the biomolecular systems considered are isomorphic to those in ordinary glass-forming material.

{"title":"The isomorphic dynamic properties of biomolecular matters and glass-forming materials","authors":"Simone Capaccioli , K.L. Ngai , Alessandro Paciaroni","doi":"10.1016/j.chemphys.2024.112543","DOIUrl":"10.1016/j.chemphys.2024.112543","url":null,"abstract":"<div><div>Glass formation is commonly found in many different kinds of materials and systems. The conventional dynamic and thermodynamic properties considered are usually associated with the structural relaxation and the transport coefficient such as viscosity. Our studies of widely different classes of glass-forming materials over several decades have led to the discovery of processes faster than the structural relaxation are strongly connected to and inseparable from the structural relaxation in dynamic and thermodynamic properties. These faster processes include the caged molecular dynamics, and a special kind of secondary relaxation with the primitive relaxation of the Coupling Model as its precursor. Overwhelming evidences from experiments and simulations supporting this universal finding can be found in the review entitled “Universal Properties of Relaxation and Diffusion in Complex Materials: Originating from Fundamental Physics with Rich Applications“, published in <em>Prog. Mater. Sci</em>. 2023, 139, 101130. Consequently any theory of glass transition is neither complete nor fundamental if these important faster processes have not been considered. In this paper we examine the dynamics and thermodynamic properties of dry, hydrated, and solvated proteins and biomolecules to find the presence of the faster processes and verify their strong connections to the structural relaxation. Thus the dynamics and thermodynamics of the processes in the biomolecular systems considered are isomorphic to those in ordinary glass-forming material.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112543"},"PeriodicalIF":2.0,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164754","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

Effect of mechanical ball milling on the microstructure and radiation shielding performance of nano-PbO 机械球磨对纳米pbo微观结构及辐射屏蔽性能的影响

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-11-28 DOI: 10.1016/j.chemphys.2024.112542

M.M. Mourad , T. Sharshar , M. Ghali , Y. Abdou , F. Elhussiny , O.M. Hemeda , H.M. Badran

This study probes the shielding efficacy of nano-PbO, examining the effects of milling on its microstructure and the consequences on X- and gamma-ray absorption. Characterization techniques, including XRD, Raman spectroscopy, TEM, and positron annihilation spectroscopy of commercial (milled for 10, 20, and 40 h) samples, as well as the synthesized PbO, reveal that milling induces a partial phase transformation from orthorhombic to tetragonal, alters particle morphology, and increases pore volume. Notably, milling does not significantly affect X-ray attenuation. The growing particle size with lower surface area, reduction of vacancy-type defects, and expanded pore size resulting from ball milling negatively influenced the probability of interaction of gamma-rays (<250 keV). Principal component analysis highlights the interplay between particle size, surface area, defect density, and pore size in determining shielding efficacy. This investigation underscores the importance of considering multiple parameters, beyond particle size, to optimize the radiation shielding performance of any material.

本研究探讨了纳米pbo的屏蔽效果，考察了铣削对其微观结构的影响以及对X射线和伽马射线吸收的影响。表征技术，包括XRD，拉曼光谱，TEM和正电子湮没光谱的商业样品（研磨10,20和40小时），以及合成的PbO，表明研磨诱导部分相变从正交向四方，改变颗粒形态，增加孔隙体积。值得注意的是，磨铣对x射线衰减没有显著影响。随着粒径的增大，表面积的减小，空位型缺陷的减少，以及球磨导致的孔径的扩大，对伽马射线相互作用的概率（<250 keV）产生了负面影响。主成分分析强调了粒径、表面积、缺陷密度和孔径在决定屏蔽效果方面的相互作用。这项研究强调了考虑多种参数的重要性，除了粒径，优化任何材料的辐射屏蔽性能。

{"title":"Effect of mechanical ball milling on the microstructure and radiation shielding performance of nano-PbO","authors":"M.M. Mourad , T. Sharshar , M. Ghali , Y. Abdou , F. Elhussiny , O.M. Hemeda , H.M. Badran","doi":"10.1016/j.chemphys.2024.112542","DOIUrl":"10.1016/j.chemphys.2024.112542","url":null,"abstract":"<div><div>This study probes the shielding efficacy of nano-PbO, examining the effects of milling on its microstructure and the consequences on X- and gamma-ray absorption. Characterization techniques, including XRD, Raman spectroscopy, TEM, and positron annihilation spectroscopy of commercial (milled for 10, 20, and 40 h) samples, as well as the synthesized PbO, reveal that milling induces a partial phase transformation from orthorhombic to tetragonal, alters particle morphology, and increases pore volume. Notably, milling does not significantly affect X-ray attenuation. The growing particle size with lower surface area, reduction of vacancy-type defects, and expanded pore size resulting from ball milling negatively influenced the probability of interaction of gamma-rays (<250 keV). Principal component analysis highlights the interplay between particle size, surface area, defect density, and pore size in determining shielding efficacy. This investigation underscores the importance of considering multiple parameters, beyond particle size, to optimize the radiation shielding performance of any material.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112542"},"PeriodicalIF":2.0,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142757499","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

Comment on “Relativistic spinless energies and thermodynamic properties of sodium dimer molecule” 对“钠二聚体分子的相对论性无自旋能和热力学性质”的评析

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-11-28 DOI: 10.1016/j.chemphys.2024.112535

Francisco M. Fernández

In this Comment we point out two incorrect results in a paper published recently in this journal. In the first place, the fact that the maximum number of vibrational energy levels is not a variable parameter of the model because it is determined by the potential-energy function and, in particular, by the dissociation energy. In the second place, we argue that the vibrational thermodynamic functions for an excited electronic state of a diatomic molecule are of no physical utility because any physical application requires the more relevant contribution of the lower electronic states to the canonical partition function. To illustrate this point we show the calculation of the equilibrium constant for the dimerization of sodium using only spectroscopic information about the ground electronic state. The theoretical expression agrees remarkably well with the available experimental data.

在这篇评论中，我们指出了最近发表在该杂志上的一篇论文中的两个不正确的结果。首先，振动能级的最大数目不是模型的可变参数，因为它是由势能函数决定的，特别是由解离能决定的。其次，我们认为双原子分子激发态的振动热力学函数没有物理效用，因为任何物理应用都需要低电子态对正则配分函数的更相关贡献。为了说明这一点，我们展示了仅使用有关基电子态的光谱信息计算钠二聚化的平衡常数。理论表达式与现有的实验数据非常吻合。

引用次数: 0

A novel eco-friendly depressant Scutellaria Baicalensis Extract SBE and its performance on flotation separation of chalcopyrite from sphalerite: A combined experimental and mechanism investigation 新型环保型抑制剂黄芩提取物SBE及其对黄铜矿与闪锌矿浮选分离效果的实验与机理研究

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-11-28 DOI: 10.1016/j.chemphys.2024.112541

Juan Yu , Xiaolin Zhang , Xinxin Liu , Xinglong Xu , Xingyu Chen , Haiyang He , Yue Zhang , Rong Peng , Peilun Shen , Dianwen Liu

This research investigates the utilization of Scutellaria Baicalensis Extract (SBE) as a depressant in the flotation separation of sphalerite and chalcopyrite with Potassium Amylxanthate (PAX) serving as the flotation collector. The feasibility of SBE as a sphalerite depressant at near neutral pH conditions was evaluated through flotation tests, and its depression mechanism was explored using contact angle measurements, zeta potential measurements, adsorption measurements and XPS analyses. Micro-flotation experiments demonstrated the efficacy of SBE as a sphalerite depressant. In artificial mixed mineral experiments, a Cu concentrate with a recovery of 92.55 % and a grade of 28.45 % Cu, and a Zn concentrate with a recovery of 94.43 % and a grade of 57.30 % Zn were obtained at an SBE concentration of 37.5 mg/L. Contact angle, zeta potential and adsorption measurements revealed that SBE was adsorbed onto both sphalerite and chalcopyrite surface, with stronger adsorption on sphalerite. The amount of SBE adsorption on sphalerite exceeded that on chalcopyrite, and SBE prevented the collector’s adsorption on sphalerite while minimally affecting chalcopyrite. XPS analysis results suggested that SBE likely acts through physical adsorption on the mineral surface.

以黄芩提取物（SBE）为抑制剂，以淀粉黄药钾（PAX）为浮选捕收剂，对闪锌矿和黄铜矿进行了浮选分离研究。通过浮选试验评价了SBE在接近中性pH条件下作为闪锌矿抑制剂的可行性，并通过接触角测量、zeta电位测量、吸附测量和XPS分析探讨了SBE的抑制机理。微浮选实验证明了SBE作为闪锌矿抑制剂的有效性。在SBE浓度为37.5 mg/L的条件下，获得了铜回收率为92.55%、品位为28.45%的铜精矿和锌回收率为94.43%、品位为57.30%的锌精矿。接触角、zeta电位和吸附测定表明，SBE在闪锌矿和黄铜矿表面均有吸附，闪锌矿表面吸附力更强。SBE在闪锌矿上的吸附量超过了在黄铜矿上的吸附量，并且SBE阻止了捕收剂对闪锌矿的吸附，而对黄铜矿的影响最小。XPS分析结果表明，SBE可能通过物理吸附在矿物表面起作用。

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引用次数: 0

Could organoaluminium complexes act as prominent TADF emitters for designing efficient diode devices? A DFT/TDA simulation study

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-11-28 DOI: 10.1016/j.chemphys.2024.112544

Jamilah A Asiri , Walid M.I. Hasan , Abdesselem Jedidi , Shaaban A. Elroby , Saadullah G. Aziz , Osman I. Osman

Theoretical calculations suggest possible designs of Thermally Activated Delayed Fluorescence (TADF) emitters using three-coordinate aluminium (Al-X₃) complexes for the design of organometal light emitting diodes. We investigate the optical properties of gas-phase and toluene-solvated Ac-Al, Ac-Al-F, Ac-Al-CN and Ac-Al-NO₂ complexes using DFT/TDA methods. All calculations were carried out using the long-range corrected ωB97XD functional with optimal ω values. Except for Ac-Al-CN contender, the aluminum atom has magnified the spin–orbit couplings between the excited singlet (S₁) and triplet (T₁) states. The decrease in the reorganization energies of Ac-Al-CN and Ac-Al-NO₂ complexes has maximized their reverse intersystem crossing rate constants. The presence of the strong electron withdrawing nitro group has further stabilized its LUMO together with improving both its oscillator strength and the emission decay rate constant. This contender is predicted to be the most prominent TADF emitter and highly promising for designing diode devises amongst the understudy complexes.

{"title":"Could organoaluminium complexes act as prominent TADF emitters for designing efficient diode devices? A DFT/TDA simulation study","authors":"Jamilah A Asiri , Walid M.I. Hasan , Abdesselem Jedidi , Shaaban A. Elroby , Saadullah G. Aziz , Osman I. Osman","doi":"10.1016/j.chemphys.2024.112544","DOIUrl":"10.1016/j.chemphys.2024.112544","url":null,"abstract":"<div><div>Theoretical calculations suggest possible designs of Thermally Activated Delayed Fluorescence (TADF) emitters using three-coordinate aluminium (Al-X<sub>3</sub>) complexes for the design of organometal light emitting diodes. We investigate the optical properties of gas-phase and toluene-solvated Ac-Al, Ac-Al-F, Ac-Al-CN and Ac-Al-NO<sub>2</sub> complexes using DFT/TDA methods. All calculations were carried out using the long-range corrected ωB97XD functional with optimal ω values. Except for Ac-Al-CN contender, the aluminum atom has magnified the spin–orbit couplings between the excited singlet (S<sub>1</sub>) and triplet (T<sub>1</sub>) states. The decrease in the reorganization energies of Ac-Al-CN and Ac-Al-NO<sub>2</sub> complexes has maximized their reverse intersystem crossing rate constants. The presence of the strong electron withdrawing nitro group has further stabilized its LUMO together with improving both its oscillator strength and the emission decay rate constant. This contender is predicted to be the most prominent TADF emitter and highly promising for designing diode devises amongst the understudy complexes.</div></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"591 ","pages":"Article 112544"},"PeriodicalIF":2.0,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164752","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

Tactfully regulating the ESIPT mechanism of novel benzazolyl-4-quinolones fluorophore by atomic electronegativity 利用原子电负性巧妙调节新型苯并唑-4-喹诺酮类荧光团的ESIPT机制

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2024-11-27 DOI: 10.1016/j.chemphys.2024.112545

Qingqing Zhang , Shun Li , Saifei Yuan , Xiaole Qiu , Chuan-Lu Yang

The effects of atomic electronegativity (O, S and Se) on the excited state intramolecular proton transfer (ESIPT) behavior of fluorescent benzazolyl-4-quinolones derivatives have been investigated theoretically. Analysis of structure parameters and infrared vibrational spectra indicate that the intramolecular hydrogen bonds (O₁H₁⋯N₁) are gradually strengthened in the first (S₁) excited state as the atomic electronegativity diminishes (O → S → Se). The topological parameters, reduced density gradient (RDG) scatter plots and interaction region indicator (IRI) isosurface further confirm our results. The energy gap of molecular orbitals reflect that the less atomic electronegativity prompt greater excited state reactivity. In addition, the constructed potential energy curves (PECs) reveal that Se substituent has lower potential barrier (0.42 kcal/mol), which is more likely to accelerate the occurrence of ESIPT process. These results show that the atomic electronegativity helps to regulate the ESIPT process, which will pave the way for the design and synthesis of ESIPT-based fluorophores in future.

从理论上研究了原子电负性（O， S和Se）对荧光苯并唑基-4-喹诺酮类衍生物激发态分子内质子转移（ESIPT）行为的影响。结构参数和红外振动谱分析表明，随着原子电负性减小（O→S→Se），分子内氢键（O1H1⋯N1）在第一（S1）激发态逐渐加强。拓扑参数、减少密度梯度（RDG）散点图和相互作用区域指示（IRI）等值面进一步证实了我们的结果。分子轨道的能隙反映了原子电负性越小，激发态反应性越强。此外，构建的势能曲线（PECs）显示，Se取代基具有较低的势垒（0.42 kcal/mol），更有可能加速ESIPT过程的发生。这些结果表明原子的电负性有助于调控ESIPT过程，这将为未来设计和合成基于ESIPT的荧光团铺平道路。

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引用次数: 0

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