Pub Date : 2024-09-03DOI: 10.1016/j.chemphys.2024.112445
Vytautas Bubilaitis, Darius Abramavicius
Calculation of nonlinear spectra of chromophore aggregates using response function theory when the number of contributing chromophores is large, and the level of excitation is high is extremely complicated. The main limitation is due to the exponential growth of computational time due to the aggregate size and number of excitations when considering an arbitrary excitation intensity. Non-perturbative calculation of spectra in this case becomes advantageous. We revisit our proposed model with exciton - exciton annihilation terms and apply it to large aggregates. We generalize the equations for both paulions and bosons with a parameter that allows smooth transition from one description to another. Intermediate statistics may also be valuable as molecular electronic excitations do not strictly obey either boson or paulion statistics. Specific approximations allow efficient calculation of pump-probe spectra for a large J aggregate.
{"title":"Compact modeling of highly excited linear aggregates using generalized quantum particles","authors":"Vytautas Bubilaitis, Darius Abramavicius","doi":"10.1016/j.chemphys.2024.112445","DOIUrl":"10.1016/j.chemphys.2024.112445","url":null,"abstract":"<div><p>Calculation of nonlinear spectra of chromophore aggregates using response function theory when the number of contributing chromophores is large, and the level of excitation is high is extremely complicated. The main limitation is due to the exponential growth of computational time due to the aggregate size and number of excitations when considering an arbitrary excitation intensity. Non-perturbative calculation of spectra in this case becomes advantageous. We revisit our proposed model with exciton - exciton annihilation terms and apply it to large aggregates. We generalize the equations for both paulions and bosons with a parameter that allows smooth transition from one description to another. Intermediate statistics may also be valuable as molecular electronic excitations do not strictly obey either boson or paulion statistics. Specific approximations allow efficient calculation of pump-probe spectra for a large J aggregate.</p></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112445"},"PeriodicalIF":2.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142173709","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}
Pub Date : 2024-09-02DOI: 10.1016/j.chemphys.2024.112440
C.A. Onate , I.B. Okon , U.E. Vincent , E. Omugbe , E.S. Eyube , J.P. Araujo
An improved Wei potential energy function as a molecular potential model has not been widely reported probably due to its physical structure. In this study, the Feinberg–Horodecki (FH) equation is examined for the improved Wei energy potential function. To validate the calculations, the Feinberg–Horodecki equation is transformed into an energy equation by putting and Numerical results are generated for some molecules using the energy equation and the molecular spectroscopic constants for and 0.1. The predicted results for the energy eigenvalues are compared with the experimental data for four halogen molecules and four gallium halides. The results revealed that the negative values of do not produce values that align with the experimental data. It is also shown that the result obtained with reproduces a better result for the improved Wei potential energy function than the result obtained with
{"title":"Molecular study of an improved Wei energy potential for the halogens and gallium halides","authors":"C.A. Onate , I.B. Okon , U.E. Vincent , E. Omugbe , E.S. Eyube , J.P. Araujo","doi":"10.1016/j.chemphys.2024.112440","DOIUrl":"10.1016/j.chemphys.2024.112440","url":null,"abstract":"<div><p>An improved Wei potential energy function as a molecular potential model has not been widely reported probably due to its physical structure. In this study, the Feinberg–Horodecki (FH) equation is examined for the improved Wei energy potential function. To validate the calculations, the Feinberg–Horodecki equation is transformed into an energy equation by putting <span><math><mrow><mi>c</mi><mo>=</mo><mn>1</mn><mo>,</mo></mrow></math></span> and <span><math><mrow><msub><mi>P</mi><mi>n</mi></msub><mo>=</mo><msub><mi>E</mi><mi>n</mi></msub><mo>.</mo></mrow></math></span> Numerical results are generated for some molecules using the energy equation and the molecular spectroscopic constants for <span><math><mrow><mi>λ</mi><mo>=</mo><mo>-</mo><mn>0.1</mn><mo>,</mo><mn>0</mn><mo>,</mo></mrow></math></span> and 0.1. The predicted results for the energy eigenvalues are compared with the experimental data for four halogen molecules and four gallium halides. The results revealed that the negative values of <span><math><mi>λ</mi></math></span> do not produce values that align with the experimental data. It is also shown that the result obtained with <span><math><mrow><mi>λ</mi><mo>=</mo><mn>0</mn></mrow></math></span> reproduces a better result for the improved Wei potential energy function than the result obtained with <span><math><mrow><mi>λ</mi><mo>=</mo><mn>0.1</mn><mo>.</mo></mrow></math></span></p></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"587 ","pages":"Article 112440"},"PeriodicalIF":2.0,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142136255","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}
Pub Date : 2024-08-30DOI: 10.1016/j.chemphys.2024.112443
Rida Fatima , A. Afaq , Muhammad Ahmed , Abdul Quader , Abu Bakar , Abdulmohsen Alruwaili
This study reports the structural, electronic, optical, phonon, thermodynamic and thermoelectric properties of (X=Mg, Sr) for photovoltaic and energy applications. We performed first principles calculations using full potential linearized augmented plane wave, FP-LAPW method implemented in Wien2k. The generalized gradient approximations of Perdew–Burke–Ernzerhof PBE-GGA, and PBE revised for solids, PBEsol, is employed for structural optimization of these lead free halide perovskites. The Birch–Murnaghan energy volume curve fitting comprehend the structural stability. The optimized lattice constant of and obtained with PBE-GGA(PBEsol) is 3.99(3.92) Å and 4.42(4.65) Å. The stability is further tested with the help of formation energy and positive phonon dispersion curves calculations. For the calculations of explicit electronic and optical properties, we also employed Tran–Blaha modified Beck–Johnson (TB-mBJ) and Strongly Constrained but Appropriately Normed, SCAN, exchange and correlations functionals. The electronic band gap of computed with PBEsol, TB-mBJ and SCAN is 1.96 eV, 5.25 eV and 2.59 eV exhibiting M- indirect band gap. The band gap energy of is 2.06 eV, 6.42 eV and 2.70 eV with PBEsol, TB-mBJ and SCAN. The indirect band gap nature of is confirmed by PBEsol and TB-mBJ while it anticipated direct band gap behavior with meta-GGA SCAN. The different optical parameters like dielectric constant, optical conductivity, energy loss function, absorption, reflectivity and refractive index are calculated to assess optical activity of both perovskites. Comprehensive electronic and optical analysis advocates the utility of and for different applications is solar technology and optoelectronic devices.
{"title":"First-Principles insights to probe structural and opto-electronic properties of AgYF3 (Y=Mg, Sr) halide perovskites with variety of DFT methods","authors":"Rida Fatima , A. Afaq , Muhammad Ahmed , Abdul Quader , Abu Bakar , Abdulmohsen Alruwaili","doi":"10.1016/j.chemphys.2024.112443","DOIUrl":"10.1016/j.chemphys.2024.112443","url":null,"abstract":"<div><p>This study reports the structural, electronic, optical, phonon, thermodynamic and thermoelectric properties of <span><math><msub><mrow><mi>AgYF</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> (X=Mg, Sr) for photovoltaic and energy applications. We performed first principles calculations using full potential linearized augmented plane wave, FP-LAPW method implemented in Wien2k. The generalized gradient approximations of Perdew–Burke–Ernzerhof PBE-GGA, and PBE revised for solids, PBEsol, is employed for structural optimization of these lead free halide perovskites. The Birch–Murnaghan energy volume curve fitting comprehend the structural stability. The optimized lattice constant of <span><math><msub><mrow><mi>AgMgF</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> and <span><math><msub><mrow><mi>AgSrF</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> obtained with PBE-GGA(PBEsol) is 3.99(3.92)<!--> <!-->Å and 4.42(4.65)<!--> <!-->Å. The stability is further tested with the help of formation energy and positive phonon dispersion curves calculations. For the calculations of explicit electronic and optical properties, we also employed Tran–Blaha modified Beck–Johnson (TB-mBJ) and Strongly Constrained but Appropriately Normed, SCAN, exchange and correlations functionals. The electronic band gap of <span><math><msub><mrow><mi>AgMgF</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> computed with PBEsol, TB-mBJ and SCAN is 1.96 eV, 5.25 eV and 2.59 eV exhibiting M-<span><math><mi>Γ</mi></math></span> indirect band gap. The band gap energy of <span><math><msub><mrow><mi>AgSrF</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> is 2.06 eV, 6.42 eV and 2.70 eV with PBEsol, TB-mBJ and SCAN. The indirect band gap nature of <span><math><msub><mrow><mi>AgSrF</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> is confirmed by PBEsol and TB-mBJ while it anticipated direct band gap behavior with meta-GGA SCAN. The different optical parameters like dielectric constant, optical conductivity, energy loss function, absorption, reflectivity and refractive index are calculated to assess optical activity of both perovskites. Comprehensive electronic and optical analysis advocates the utility of <span><math><msub><mrow><mi>AgMgF</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> and <span><math><msub><mrow><mi>AgSrF</mi></mrow><mrow><mn>3</mn></mrow></msub></math></span> for different applications is solar technology and optoelectronic devices.</p></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112443"},"PeriodicalIF":2.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142149410","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}
The unique structural properties of two-dimensional materials make them promising for energy storage applications. This work theoretically predicts for the first time that Monolayer VOPO4 (MNL VOPO4), exfoliated from the delithiated phase of tetragonal LiVOPO4, is stable at room temperature, exhibiting excellent thermodynamic and kinetic stability, thus making it a promising high-capacity anode material for sodium-ion batteries (SIBs). Compared to bulk VOPO4, the monolayer structure significantly reduces the sodium ion migration energy barrier from 1.006 to 0.0795 eV, thereby markedly enhancing sodium ion migration kinetics. MNL VOPO4 can adsorb up to 32 sodium ions, corresponding to a theoretical capacity of 634.88 mA h g−1 and an energy density of 895.18 Wh kg−1. Furthermore, the excellent structural stability of MNL VOPO4 favors its cycling performance during charge and discharge processes. This work provides theoretical insights for better utilizing and developing multi-atomic phosphate compounds as electrode materials for secondary batteries.
{"title":"Electrochemical sodium storage properties in monolayer VOPO4: A density functional theory prediction","authors":"Jinggao Wu , Cuirong Deng , Chanyu Zhong , Jing Huang","doi":"10.1016/j.chemphys.2024.112442","DOIUrl":"10.1016/j.chemphys.2024.112442","url":null,"abstract":"<div><p>The unique structural properties of two-dimensional materials make them promising for energy storage applications. This work theoretically predicts for the first time that Monolayer VOPO<sub>4</sub> (MNL VOPO<sub>4</sub>), exfoliated from the delithiated phase of tetragonal LiVOPO<sub>4</sub>, is stable at room temperature, exhibiting excellent thermodynamic and kinetic stability, thus making it a promising high-capacity anode material for sodium-ion batteries (SIBs). Compared to bulk VOPO<sub>4</sub>, the monolayer structure significantly reduces the sodium ion migration energy barrier from 1.006 to 0.0795 eV, thereby markedly enhancing sodium ion migration kinetics. MNL VOPO<sub>4</sub> can adsorb up to 32 sodium ions, corresponding to a theoretical capacity of 634.88 mA h g<sup>−1</sup> and an energy density of 895.18 Wh kg<sup>−1</sup>. Furthermore, the excellent structural stability of MNL VOPO<sub>4</sub> favors its cycling performance during charge and discharge processes. This work provides theoretical insights for better utilizing and developing multi-atomic phosphate compounds as electrode materials for secondary batteries.</p></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"587 ","pages":"Article 112442"},"PeriodicalIF":2.0,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142121978","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}
Pub Date : 2024-08-29DOI: 10.1016/j.chemphys.2024.112437
Qaiser Rafiq , Sikander Azam , Muhammad Jawad , Faisal Nazeer , Islam H. El Azab , Gaber A.M. Mersal
The remarkable potential of double perovskite materials, characterized by lead-free, non-toxic attributes and robust dynamical stability, positions them as highly promising candidates for both thermoelectric and optoelectronic applications. In light of this, a comprehensive investigation is undertaken through density functional theory to thoroughly explore the optoelectronic and transport characteristics of Cs2LiBi (X = Br, I) double perovskite materials. To ascertain dynamic stability, phonon dispersion band structures are computed, and the structural stability is evaluated through the tolerance factor. The resulting band structures reveal narrow band gaps of 3.45 eV and 1.79 eV for the Br and Indium-based DPs, respectively. These narrow band gaps hold significant importance for applications such as ultraviolet detectors and other optoelectronic devices that function in the visible and UV-light spectrum. Notably, absorption peaks of maximal intensity emerge at 5.1 eV (76 nm) and 4.0 eV (67 nm) for the Br and Indium-based double perovskites, respectively. Furthermore, a comprehensive analysis of thermoelectric behavior is conducted, encompassing the figure of merit, power factor, Seebeck coefficient, and the ratio of electrical to thermal conductivity across a temperature range of 50–800 K. The exceptionally low lattice vibration values, coupled with a substantial enhancement in the thermoelectric figure of merit (ZT), notably underscore their significance for advanced thermoelectric generator applications.
双包晶材料具有无铅、无毒和动态稳定性强的特点,其巨大的潜力使其成为热电和光电应用领域极具潜力的候选材料。有鉴于此,我们通过密度泛函理论对 Cs2LiBiX6(X = Br,I)双包晶材料的光电和传输特性进行了全面研究。为了确定动态稳定性,计算了声子色散带结构,并通过容限因子评估了结构稳定性。计算得出的带状结构显示,溴基和铟基 DP 的窄带隙分别为 3.45 eV 和 1.79 eV。这些窄带隙对于紫外线探测器和其他在可见光和紫外线光谱下工作的光电器件等应用具有重要意义。值得注意的是,硼基和铟基双包晶石的最大吸收峰分别出现在 5.1 eV(76 纳米)和 4.0 eV(67 纳米)处。此外,还对热电行为进行了全面分析,包括优点系数、功率因数、塞贝克系数以及 50-800 K 温度范围内的电导率与热导率之比。异常低的晶格振动值以及热电优点系数(ZT)的大幅提高,显著强调了它们对先进热电发生器应用的重要意义。
{"title":"Computational investigation of electronic, thermoelectric, and optical properties in Cs2LiBiX6(X = Br, I) for energy harvesting applications","authors":"Qaiser Rafiq , Sikander Azam , Muhammad Jawad , Faisal Nazeer , Islam H. El Azab , Gaber A.M. Mersal","doi":"10.1016/j.chemphys.2024.112437","DOIUrl":"10.1016/j.chemphys.2024.112437","url":null,"abstract":"<div><p>The remarkable potential of double perovskite materials, characterized by lead-free, non-toxic attributes and robust dynamical stability, positions them as highly promising candidates for both thermoelectric and optoelectronic applications. In light of this, a comprehensive investigation is undertaken through density functional theory to thoroughly explore the optoelectronic and transport characteristics of Cs<sub>2</sub>LiBi<span><math><mrow><msub><mi>X</mi><mn>6</mn></msub></mrow></math></span> (X = Br, I) double perovskite materials. To ascertain dynamic stability, phonon dispersion band structures are computed, and the structural stability is evaluated through the tolerance factor. The resulting band structures reveal narrow band gaps of 3.45 eV and 1.79 eV for the Br and Indium-based DPs, respectively. These narrow band gaps hold significant importance for applications such as ultraviolet detectors and other optoelectronic devices that function in the visible and UV-light spectrum. Notably, absorption peaks of maximal intensity emerge at 5.1 eV (76 nm) and 4.0 eV (67 nm) for the Br and Indium-based double perovskites, respectively. Furthermore, a comprehensive analysis of thermoelectric behavior is conducted, encompassing the figure of merit, power factor, Seebeck coefficient, and the ratio of electrical to thermal conductivity across a temperature range of 50–800 K. The exceptionally low lattice vibration values, coupled with a substantial enhancement in the thermoelectric figure of merit (ZT), notably underscore their significance for advanced thermoelectric generator applications.</p></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112437"},"PeriodicalIF":2.0,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142239779","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}
Pub Date : 2024-08-28DOI: 10.1016/j.chemphys.2024.112427
Muhammad Ahsan Ali Abbas , Sikandar Azam , Waqas Ahmad , Maryam Naeem , Qaiser Rafiq , Mohammad Gousuddin , Dalal A. Alshammari , Islam H. El Azab
Gadolinium silicate, (Gd2SiO5) co-doped with Ce and Eu has been found to exhibit enhanced luminescence efficiency, which makes it a promising material for use in scintillators and phosphors. It has excellent scintillation properties such as high density and high Zeff. In this study, we used density functional theory (DFT) calculations within the Wien2k software to investigate the effect of Ce and Eu concentration and native defects on the electronic structure and optical properties of Ce and Eu co-doped Gd2SiO5. We utilized the DFT + U method to treat the localized 4f electrons of Ce and Eu. Our results indicate that the electronic structure and optical properties of Ce and Eu co-doped Gd2SiO5 are significantly affected by the concentration of the dopants and presence of native defects. We found that increasing the concentration of Ce and Eu dopants leads to a shift in the bandgap to lower energies, resulting in enhanced absorption and emission spectra. Moreover, our calculations reveal that presence of oxygen vacancies and Gd interstitials can induce new defect levels in the bandgap, which may affect the luminescence properties of the material. Our study provides valuable insights into the atomic-level mechanisms that govern the luminescence properties of Ce and Eu co-doped Gd2SiO5 which can aid in the design and optimization of luminescent materials for various applications.
研究发现,与 Ce 和 Eu 共掺的硅酸钆(Gd2SiO5)具有更高的发光效率,这使其成为一种有望用于闪烁体和荧光粉的材料。它具有高密度和高 Zeff 等优异的闪烁特性。在本研究中,我们利用 Wien2k 软件中的密度泛函理论(DFT)计算,研究了 Ce 和 Eu 浓度以及原生缺陷对 Ce 和 Eu 共掺杂 Gd2SiO5 的电子结构和光学特性的影响。我们利用 DFT + U 方法处理了 Ce 和 Eu 的局域 4f 电子。结果表明,掺杂 Ce 和 Eu 的 Gd2SiO5 的电子结构和光学性质受到掺杂剂浓度和原生缺陷存在的显著影响。我们发现,掺杂 Ce 和 Eu 的浓度增加会导致带隙向低能量方向移动,从而增强吸收和发射光谱。此外,我们的计算还发现,氧空位和钆间隙的存在会在带隙中诱发新的缺陷水平,从而影响材料的发光特性。我们的研究为了解支配掺杂 Ce 和 Eu 的 Gd2SiO5 发光特性的原子级机制提供了宝贵的见解,有助于设计和优化各种应用的发光材料。
{"title":"Investigation of optical properties of Ce and Eu-doped Gd2SiO5 insights from GGA + U calculations","authors":"Muhammad Ahsan Ali Abbas , Sikandar Azam , Waqas Ahmad , Maryam Naeem , Qaiser Rafiq , Mohammad Gousuddin , Dalal A. Alshammari , Islam H. El Azab","doi":"10.1016/j.chemphys.2024.112427","DOIUrl":"10.1016/j.chemphys.2024.112427","url":null,"abstract":"<div><p>Gadolinium silicate, (Gd<sub>2</sub>SiO<sub>5</sub>) co-doped with Ce and Eu has been found to exhibit enhanced luminescence efficiency, which makes it a promising material for use in scintillators and phosphors. It has excellent scintillation properties such as high density and high Zeff. In this study, we used density functional theory (DFT) calculations within the Wien2k software to investigate the effect of Ce and Eu concentration and native defects on the electronic structure and optical properties of Ce and Eu co-doped Gd<sub>2</sub>SiO<sub>5</sub>. We utilized the DFT + U method to treat the localized 4f electrons of Ce and Eu. Our results indicate that the electronic structure and optical properties of Ce and Eu co-doped Gd<sub>2</sub>SiO<sub>5</sub> are significantly affected by the concentration of the dopants and presence of native defects. We found that increasing the concentration of Ce and Eu dopants leads to a shift in the bandgap to lower energies, resulting in enhanced absorption and emission spectra. Moreover, our calculations reveal that presence of oxygen vacancies and Gd interstitials can induce new defect levels in the bandgap, which may affect the luminescence properties of the material. Our study provides valuable insights into the atomic-level mechanisms that govern the luminescence properties of Ce and Eu co-doped Gd<sub>2</sub>SiO<sub>5</sub> which can aid in the design and optimization of luminescent materials for various applications.</p></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112427"},"PeriodicalIF":2.0,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142149411","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}
Pub Date : 2024-08-27DOI: 10.1016/j.chemphys.2024.112439
Seçil Sarı , Nihat Karakuş
Dye-sensitized solar cells (DSSCs) are cost-effective photovoltaic devices that convert solar energy into electricity using a dye sensitizer, TiO2 photoanode, electrolyte, and counter electrode. This study investigates the impact of substituents on the performance of naphthoquinone-based dye sensitizers in DSSCs. We analyzed various naphthoquinone derivatives’ electronic structures and light absorption properties using DFT and TD-DFT. Our results demonstrate that electron-donating groups enhance DSSC performance by improving light absorption and electron injection. Specifically, naphthoquinone derivatives with methoxy (Dye-2) and methyl (Dye-3) groups showed superior properties. TD-DFT analysis revealed high molar extinction coefficients over a broad spectrum, making these dyes efficient at capturing sunlight. Additionally, these dyes effectively interact with TiO2, which is crucial for photostability and photovoltaic performance. In conclusion, naphthoquinone derivatives with electron-donating groups significantly improve DSSC performance, with Dye-2 and Dye-3 being strong candidates for high-performance applications.
{"title":"Effect of electron-donating and -withdrawing substitutions in naphthoquinone sensitizers: The structure engineering of dyes for DSSCs in Quantum Chemical Study","authors":"Seçil Sarı , Nihat Karakuş","doi":"10.1016/j.chemphys.2024.112439","DOIUrl":"10.1016/j.chemphys.2024.112439","url":null,"abstract":"<div><p>Dye-sensitized solar cells (DSSCs) are cost-effective photovoltaic devices that convert solar energy into electricity using a dye sensitizer, TiO<sub>2</sub> photoanode, electrolyte, and counter electrode. This study investigates the impact of substituents on the performance of naphthoquinone-based dye sensitizers in DSSCs. We analyzed various naphthoquinone derivatives’ electronic structures and light absorption properties using DFT and TD-DFT. Our results demonstrate that electron-donating groups enhance DSSC performance by improving light absorption and electron injection. Specifically, naphthoquinone derivatives with methoxy (Dye-2) and methyl (Dye-3) groups showed superior properties. TD-DFT analysis revealed high molar extinction coefficients over a broad spectrum, making these dyes efficient at capturing sunlight. Additionally, these dyes effectively interact with TiO<sub>2</sub>, which is crucial for photostability and photovoltaic performance. In conclusion, naphthoquinone derivatives with electron-donating groups significantly improve DSSC performance, with Dye-2 and Dye-3 being strong candidates for high-performance applications.</p></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"587 ","pages":"Article 112439"},"PeriodicalIF":2.0,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142136254","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}
Pub Date : 2024-08-24DOI: 10.1016/j.chemphys.2024.112438
Xue Yang, Mengyu Lin, Jiumei Chu, Dianquan Dong
The unique properties of cesium compounds have garnered increasing attention, among which Cs2Ti6O13 shows great potential for applications. This paper synthesized Cs2Ti6O13(CTO-3) using a template-assisted solvothermal method with cesium carbonate as the cesium source and tetrabutyl titanate as the titanium source. Among them, F127 and hexadecylamine are used as template agents to modulate the surface morphology and hydrophilicity of the precursor. The cesium ion sieve H2Ti6O13 (HTO-3) synthesized after hydrochloric acid pickling has a large specific surface area and good hydrophilicity. This structure is conducive to the ion exchange between Cs+ and H+, resulting in a fast adsorption rate. It is completed within 2 h, and the adsorption capacity reaches 360 mg/g, which is significantly greater than that of the traditional high-temperature solid-phase method. The adsorption process of Cs+ on HTO-3 is more consistent with the pseudo-second-order kinetic equation model, and the adsorption process is chemical adsorption. HTO-3 exhibited good selectivity and cycle stability. At the fifth time of the adsorption-resolution cycle, the adsorption capacity was 87.1 % of the first time.
{"title":"Preparation of highly hydrophilic cesium ion sieve and its performance in adsorbing Cs+","authors":"Xue Yang, Mengyu Lin, Jiumei Chu, Dianquan Dong","doi":"10.1016/j.chemphys.2024.112438","DOIUrl":"10.1016/j.chemphys.2024.112438","url":null,"abstract":"<div><p>The unique properties of cesium compounds have garnered increasing attention, among which Cs<sub>2</sub>Ti<sub>6</sub>O<sub>13</sub> shows great potential for applications. This paper synthesized Cs<sub>2</sub>Ti<sub>6</sub>O<sub>13</sub>(CTO-3) using a template-assisted solvothermal method with cesium carbonate as the cesium source and tetrabutyl titanate as the titanium source. Among them, F127 and hexadecylamine are used as template agents to modulate the surface morphology and hydrophilicity of the precursor. The cesium ion sieve H<sub>2</sub>Ti<sub>6</sub>O<sub>13</sub> (HTO-3) synthesized after hydrochloric acid pickling has a large specific surface area and good hydrophilicity. This structure is conducive to the ion exchange between Cs<sup>+</sup> and H<sup>+</sup>, resulting in a fast adsorption rate. It is completed within 2 h, and the adsorption capacity reaches 360 mg/g, which is significantly greater than that of the traditional high-temperature solid-phase method. The adsorption process of Cs<sup>+</sup> on HTO-3 is more consistent with the pseudo-second-order kinetic equation model, and the adsorption process is chemical adsorption. HTO-3 exhibited good selectivity and cycle stability. At the fifth time of the adsorption-resolution cycle, the adsorption capacity was 87.1 % of the first time.</p></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"588 ","pages":"Article 112438"},"PeriodicalIF":2.0,"publicationDate":"2024-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142173441","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}
Pub Date : 2024-08-21DOI: 10.1016/j.chemphys.2024.112418
H.F. Sun, S.P. Sun, Y.R. Wang, Y. Zhang
The surface relaxations, surface stability, electronic structures, and equilibrium morphology of D52-La2O3 were analyzed by means of first-principles calculations. The stoichiometric surfaces of D52-La2O3 possess thermodynamic energies of the following order: (0 0 1) < (1 1 0) < (1 0 0). Changes in temperature and the partial pressure of oxygen were employed to determine the energy of the non-stoichiometric surfaces. The results indicated that the energies of the (ns-1La1O)-terminated (1 0 0) and (ns-1La)-terminated (0 0 1) surfaces increased with increasing oxygen partial pressures and decreased with temperatures, whereas the (ns-1O)-terminated (0 0 1) and (ns-1O)-terminated (1 0 0) surfaces exhibited the reverse rule. According to the calculated density of states, surface relaxations primarily impact the surface electronic structures. The Gibbs-Wulff model was used to forecast the equilibrium morphology of D52-La2O3, which followed in comparison with other’s experimental findings.
{"title":"Exploring the low-index surfaces of D52-La2O3 from the first-principles calculations","authors":"H.F. Sun, S.P. Sun, Y.R. Wang, Y. Zhang","doi":"10.1016/j.chemphys.2024.112418","DOIUrl":"10.1016/j.chemphys.2024.112418","url":null,"abstract":"<div><p>The surface relaxations, surface stability, electronic structures, and equilibrium morphology of D5<sub>2</sub>-La<sub>2</sub>O<sub>3</sub> were analyzed by means of first-principles calculations. The stoichiometric surfaces of D5<sub>2</sub>-La<sub>2</sub>O<sub>3</sub> possess thermodynamic energies of the following order: (0<!--> <!-->0<!--> <!-->1) < (1<!--> <!-->1<!--> <!-->0) < (1<!--> <!-->0<!--> <!-->0). Changes in temperature and the partial pressure of oxygen were employed to determine the energy of the non-stoichiometric surfaces. The results indicated that the energies of the (ns-1La1O)-terminated (1<!--> <!-->0<!--> <!-->0) and (ns-1La)-terminated (0<!--> <!-->0<!--> <!-->1) surfaces increased with increasing oxygen partial pressures and decreased with temperatures, whereas the (ns-1O)-terminated (0<!--> <!-->0<!--> <!-->1) and (ns-1O)-terminated (1<!--> <!-->0<!--> <!-->0) surfaces exhibited the reverse rule. According to the calculated density of states, surface relaxations primarily impact the surface electronic structures. The Gibbs-Wulff model was used to forecast the equilibrium morphology of D5<sub>2</sub>-La<sub>2</sub>O<sub>3</sub>, which followed in comparison with other’s experimental findings.</p></div>","PeriodicalId":272,"journal":{"name":"Chemical Physics","volume":"587 ","pages":"Article 112418"},"PeriodicalIF":2.0,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142117383","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}