The most commonly used and studied hybrid halide perovskite is ABX_3, where A usually stands for CH_3NH_3, B for Pb, and X for I. A lead-free perovskite with high stability and ideal electronic band structure would be...The most commonly used and studied hybrid halide perovskite is ABX_3, where A usually stands for CH_3NH_3, B for Pb, and X for I. A lead-free perovskite with high stability and ideal electronic band structure would be of essence, especially considering the toxicity of lead. In this work, we have considered 11 metal elements for the B site and three halide elements(Cl, Br, and I) including various combinations among the three halides for the X site. A total number of 99 hybrid perovskites are studied to understand how the crystal structure, band gap and stability can be tuned by the chemistry modification, i.e., the replacement of toxic element, Pb in the original MAPbX_3, with non-toxic metal elements. We find that the favorable substitutes for Pb in MAPbI_3 are Ge and Sn.展开更多
The structural and thermodynamic （PCTAs） in the ideal gas state at 298.15 K and 1.013 properties of 75 polychlorinated thianthrenes ×10^5 Pa have been calculated at the B3LYP/6- 31G＊ level using Gaussian 98 pr...The structural and thermodynamic （PCTAs） in the ideal gas state at 298.15 K and 1.013 properties of 75 polychlorinated thianthrenes ×10^5 Pa have been calculated at the B3LYP/6- 31G＊ level using Gaussian 98 program. Based on the output data of Gaussian, the isodesmic reactions were designed to calculate standard enthalpy of formation （△fH^θ） and standard free energy of formation （△fH^θ） of PCTAs congeners. The relations of these thermodynamic parameters with the number and position of C1 atom substitution （Npcs） were discussed, and it was found that there exists high correlation between thermodynamic parameters （total energy （TE）, zero-point vibrational energy （ZPE）, thermal correction to energy （Eth）, heat capacity at constant volume （Cv^θ）, entropy （S^θ）, enthalpy （H^θ）, free energy （G^θ）, standard enthalpies of formation （△fH^θ） and standard Gibbs energies of formation （△fG^θ）） and Npcs. On the basis of the relative magnitude of their △fG^θ, the order of relative stability of PCTA congeners was theoretically proposed. In addition, the correlations between structural parameters and Npcs were also discussed. The good correlations were found between molecular average polarizability （α）, energy of the highest occupied molecular orbital （EHOMO）, molecular volume （Vm） and Npcs, and all R^2 values are larger than 0.95. Moreover, it was supposed that the isomer groups with higher toxicity should be Tri-CTA and TCTA.展开更多
The preparation of high-efficiency phosphor is the key to the construction of white light-emitting diode(WLED)devices and their application in indoor photovoltaics.Compared with YVO_(4),InVO_(4)is not suitable as the ...The preparation of high-efficiency phosphor is the key to the construction of white light-emitting diode(WLED)devices and their application in indoor photovoltaics.Compared with YVO_(4),InVO_(4)is not suitable as the host material of lanthanide ions because of its strong self-luminescence.Here,the work focused on combining the broadband emission from InVO_(4)and the red luminescence from YVO_(4):Eu^(3+)to obtain enhanced and stable multicolor luminescence.The band structure,density of state,and optical properties were studied by density functional theory.The spectral configuration of YVO_(4):In^(3+)/Eu^(3+)with(112)surface appears to be broadening and redshifts with increasing layer number.When the In^(3+)concentration is 3.5 mol%,the YVO_(4):30%Eu^(3+)/In^(3+)emits the strongest light.The Judd-Ofelt parameterΩ2 of YVO_(4):In^(3+)/Eu^(3+)increases with increaing In^(3+)concentration,indicating that the symmetry decreases.By adjusting In^(3+)/Eu^(3+)contents,the YVO_(4):In^(3+)/Eu^(3+)not only can emit white light with a color rendering index of 95,but also can be used as high-efficiency red phosphor to build WLED devices with blue emitting N/Tb codoped carbon quantum dots(CQDs-N:Tb^(3+))and green emitting MOF:Tb^(3+)(MOF=metal organic framework),for which the color rendering index can also reach 95 and the color temperature is 5549 K.The manufactured WLED devices were further used to excite the silicon solar cell and make it show good photoelectric characteristics.展开更多
In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properti...In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properties of the complexes. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods have been used. The ground state geometries, binding energies, spectral properties (UV-vis), frontier molecular orbitals (FMOs) analysis, charge analysis and natural bond orbital (NBO) have been investigated. The geometrical parameters are in good agreement with the available experimental data. The metal-ligand binding energies are 1 order of magnitude larger than the physisorption energy of a benzene-1, 2-dthiolate molecule on a metallic surface. The electronic structures of the first raw transition metal series from V to Co have been elucidated by UV-vis spectroscopic using DFT calculations. In accordance with experiment the calculated electronic spectra of these tris complexes show bands at 522, 565, 559, 546 and 863 nm for V3+, Cr3+, Mn3+, Fe3+ and Co3+ respectively which are mainly attributed to ligand to metal charge transfer (LMCT) transitions. The electronic properties analysis shows that the highest occupied molecular orbital (HOMO) is mainly centered on metal coordinated sulfur atoms whereas the lowest unoccupied molecular orbital (LUMO) is mainly located on the metal surface. From calculation of intramolecular interactions and electron delocalization by natural bond orbital (NBO) analysis, the stability of the complexes was estimated. The NBO results showed significant charge transfer from sulfur to central metal ions in the complexes, as well as to the benzene. The calculated charges on metal ions are also reported at various charge schemes. The calculations show encouraging agreement with the available experimental data.展开更多
A new two-dimensional atomic crystal,monolayer cuprous telluride(Cu2Te)has been fabricated on a grapheneSi C(0001)substrate by molecular beam epitaxy(MBE).The low-energy electron diffraction(LEED)characterization show...A new two-dimensional atomic crystal,monolayer cuprous telluride(Cu2Te)has been fabricated on a grapheneSi C(0001)substrate by molecular beam epitaxy(MBE).The low-energy electron diffraction(LEED)characterization shows that the monolayer Cu2Te forms a √3×√3superstructure with respect to the graphene substrate.The atomic structure of the monolayer Cu2Te is investigated through a combination of scanning tunneling microscopy(STM)experiments and density functional theory(DFT)calculations.The stoichiometry of the Cu2Te sample is verified by x-ray photoelectron spectroscopy(XPS)measurement.The angle-resolved photoemission spectroscopy(ARPES)data present the electronic band structure of the sample,which is in good agreement with the calculated results.Furthermore,air-exposure experiments reveal the chemical stability of the monolayer Cu2Te.The fabrication of this new 2D material with a particular structure may bring new physical properties for future applications.展开更多
Density functional theory (DFT) method has been employed to study the effect of nitroamino group as a substituent in cyclopentane and cyclohexane, which usually construct the polycyclic or caged nitra-mines. Molecular...Density functional theory (DFT) method has been employed to study the effect of nitroamino group as a substituent in cyclopentane and cyclohexane, which usually construct the polycyclic or caged nitra-mines. Molecular structures were investigated at the B3LYP/6-31G** level, and isodesmic reactions were designed for calculating the group interactions. The results show that the group interactions ac-cord with the group additivity, increasing with the increasing number of nitroamino groups. The dis-tance between substituents influences the interactions. Detonation performances were evaluated by the Kamlet-Jacobs equations based on the predicted densities and heats of formation, while thermal stability and pyrolysis mechanism were studied by the computations of bond dissociation energy (BDE). It is found that the contributions of nitroamino groups to the detonation heat, detonation velocity, detonation pressure, and stability all deviate from the group additivity. Only 3a, 3b, and 9a-9c may be novel potential candidates of high energy density materials (HEDMs) according to the quantitative cri-teria of HEDM (ρ≈ 1.9 g/cm3, D ≈ 9.0 km/s, P ≈ 40.0 GPa). Stability decreases with the increasing number of N-NO2 groups, and homolysis of N-NO2 bond is the initial step in the thermolysis of the title com-pounds. Coupled with the demand of thermal stability (BDE > 20 kcal/mol), only 1,2,4-trinitrotriazacy-clohexane and 1,2,4,5-tetranitrotetraazacyclohexane are suggested as feasible energetic materials. These results may provide basic information for the molecular design of HEDMs.展开更多
Based on the octadecahedron of eleven-vertex closo-borane, the eleven-vertex closo-heteroborane was suggested with nonmetallic atoms instead of the different nonequivalent boron, and the stabilities were predicted at ...Based on the octadecahedron of eleven-vertex closo-borane, the eleven-vertex closo-heteroborane was suggested with nonmetallic atoms instead of the different nonequivalent boron, and the stabilities were predicted at G96PW91/6-31＋G（3d,2p） level. The small heteroatoms, C, N, O, preferentially occupy vertex 2 with the absolutely lowest relative energy to form the high stabilization closo-heteroboranes. They cap four-membered rings to satisfy the geometrical demand of short B--Z bonds. The electron attractions from the vicinal boron atoms make the frameworks shrink. Differently, Si and Ge preferentially substitute for boron at vertex 1 with six tight B--Z bonds and form stabilized molecules. P, As, S, and Se tend to occupy vertex 4 and the optimized structures belong to the nido configura- tions. In contrast to high electronegative heteroatoms, S and Se transfer less negative charges to framework and the electropositive heteroatoms, Si and Ge transfer more negative charges to framework to form the delocalization structures. The HOMO-LUMO gaps show that most of predicted clusters possess chemical stabilities. The substitutions of heteroatoms for boron atoms in eleven-vertex closo-heteroboranes are consistent with the topological charge stabilization rule proposed by Gimarc.展开更多
The construction of stable and efficient materials that emit blue and green light remains a challenge.Among the blue light materials reported,metal-organic framework(MOF)materials are rarely reported as blue phosphors...The construction of stable and efficient materials that emit blue and green light remains a challenge.Among the blue light materials reported,metal-organic framework(MOF)materials are rarely reported as blue phosphors due to their weak luminescence intensity.Based on the construction of CsPbBr_(3)@MOF(CPB@MOF),an innovative idea was proposed to simultaneously enhance the green luminescence of CPB and the blue luminescence of MOF through the interaction between CPB and MOF for the first time.As expected,the blue luminescence from CPB:7%SCN−@0.5%MOF:Eu as well as the green luminescence from 5%CPB:7%SCN−@MOF:Eu was sufficient to construct high-performance light-emitting diode(LED)devices and further excite solar cells to generate stable photoelectric signals.The white LED(WLED)device with excellent color quality(color rendering index(CRI)=96.2)and correlated color temperature(CCT=9688 K)can be constructed by using the obtained blue-emitting CPB:7%SCN-@0.5%MOF:Eu,green-emitting 5%CPB:7%SCN−@MOF:Eu,and red-emitting PPB:30%Mn^(2+).The density functional theory(DFT)theoretical calculation results indicate that the p orbital of Pb plays the major role in the conduction band,and the p orbital of Br plays the major role in the valance band of CPB and CPB:SCN−.While the p orbital of O plays the major role in both the conduction band and valance band of MOF.The heat capacity of CPB and CPB:SCN−separately reaches the Dulong–Petit limit at 200 and 400 K,indicating that the thermal stability of CsPbBr_(3)increases after SCN−doping.展开更多
A plane wave density functional theory method was used to investigate the adsorption properties of isolated alkali metal atoms, including Li, Na, K, Rb and Cs on-top of the F 0 s defective center of MgO（001） surface...A plane wave density functional theory method was used to investigate the adsorption properties of isolated alkali metal atoms, including Li, Na, K, Rb and Cs on-top of the F 0 s defective center of MgO（001） surface. Among all the alkali metals, the lithium atom binds most strongly with the highest adsorption energy of 0.67 eV and the shortest distance of about 0.257 nm between metal and the surface, the binding energy for the sodium atom comes second, and just half of this value for the other alkali metal atoms. The relatively strong interaction of Li with the F 0 s center can be explained by a more covalent bonding involved, evidenced by results of both the projected density of states and the projected charge density. The bonding mechanism is discussed in detail.展开更多
基金the Shanghai Sailing(YANG FAN)Program(No.16YF1406000)the Startup Fund from Shanghai Jiao Tong University
文摘The most commonly used and studied hybrid halide perovskite is ABX_3, where A usually stands for CH_3NH_3, B for Pb, and X for I. A lead-free perovskite with high stability and ideal electronic band structure would be of essence, especially considering the toxicity of lead. In this work, we have considered 11 metal elements for the B site and three halide elements(Cl, Br, and I) including various combinations among the three halides for the X site. A total number of 99 hybrid perovskites are studied to understand how the crystal structure, band gap and stability can be tuned by the chemistry modification, i.e., the replacement of toxic element, Pb in the original MAPbX_3, with non-toxic metal elements. We find that the favorable substitutes for Pb in MAPbI_3 are Ge and Sn.
基金the National Natural Science Foundation of China(No.20737001 and 20477018)
文摘The structural and thermodynamic （PCTAs） in the ideal gas state at 298.15 K and 1.013 properties of 75 polychlorinated thianthrenes ×10^5 Pa have been calculated at the B3LYP/6- 31G＊ level using Gaussian 98 program. Based on the output data of Gaussian, the isodesmic reactions were designed to calculate standard enthalpy of formation （△fH^θ） and standard free energy of formation （△fH^θ） of PCTAs congeners. The relations of these thermodynamic parameters with the number and position of C1 atom substitution （Npcs） were discussed, and it was found that there exists high correlation between thermodynamic parameters （total energy （TE）, zero-point vibrational energy （ZPE）, thermal correction to energy （Eth）, heat capacity at constant volume （Cv^θ）, entropy （S^θ）, enthalpy （H^θ）, free energy （G^θ）, standard enthalpies of formation （△fH^θ） and standard Gibbs energies of formation （△fG^θ）） and Npcs. On the basis of the relative magnitude of their △fG^θ, the order of relative stability of PCTA congeners was theoretically proposed. In addition, the correlations between structural parameters and Npcs were also discussed. The good correlations were found between molecular average polarizability （α）, energy of the highest occupied molecular orbital （EHOMO）, molecular volume （Vm） and Npcs, and all R^2 values are larger than 0.95. Moreover, it was supposed that the isomer groups with higher toxicity should be Tri-CTA and TCTA.
基金supported by the National Natural Science Foundation of China(No.22271080).
文摘The preparation of high-efficiency phosphor is the key to the construction of white light-emitting diode(WLED)devices and their application in indoor photovoltaics.Compared with YVO_(4),InVO_(4)is not suitable as the host material of lanthanide ions because of its strong self-luminescence.Here,the work focused on combining the broadband emission from InVO_(4)and the red luminescence from YVO_(4):Eu^(3+)to obtain enhanced and stable multicolor luminescence.The band structure,density of state,and optical properties were studied by density functional theory.The spectral configuration of YVO_(4):In^(3+)/Eu^(3+)with(112)surface appears to be broadening and redshifts with increasing layer number.When the In^(3+)concentration is 3.5 mol%,the YVO_(4):30%Eu^(3+)/In^(3+)emits the strongest light.The Judd-Ofelt parameterΩ2 of YVO_(4):In^(3+)/Eu^(3+)increases with increaing In^(3+)concentration,indicating that the symmetry decreases.By adjusting In^(3+)/Eu^(3+)contents,the YVO_(4):In^(3+)/Eu^(3+)not only can emit white light with a color rendering index of 95,but also can be used as high-efficiency red phosphor to build WLED devices with blue emitting N/Tb codoped carbon quantum dots(CQDs-N:Tb^(3+))and green emitting MOF:Tb^(3+)(MOF=metal organic framework),for which the color rendering index can also reach 95 and the color temperature is 5549 K.The manufactured WLED devices were further used to excite the silicon solar cell and make it show good photoelectric characteristics.
文摘In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properties of the complexes. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods have been used. The ground state geometries, binding energies, spectral properties (UV-vis), frontier molecular orbitals (FMOs) analysis, charge analysis and natural bond orbital (NBO) have been investigated. The geometrical parameters are in good agreement with the available experimental data. The metal-ligand binding energies are 1 order of magnitude larger than the physisorption energy of a benzene-1, 2-dthiolate molecule on a metallic surface. The electronic structures of the first raw transition metal series from V to Co have been elucidated by UV-vis spectroscopic using DFT calculations. In accordance with experiment the calculated electronic spectra of these tris complexes show bands at 522, 565, 559, 546 and 863 nm for V3+, Cr3+, Mn3+, Fe3+ and Co3+ respectively which are mainly attributed to ligand to metal charge transfer (LMCT) transitions. The electronic properties analysis shows that the highest occupied molecular orbital (HOMO) is mainly centered on metal coordinated sulfur atoms whereas the lowest unoccupied molecular orbital (LUMO) is mainly located on the metal surface. From calculation of intramolecular interactions and electron delocalization by natural bond orbital (NBO) analysis, the stability of the complexes was estimated. The NBO results showed significant charge transfer from sulfur to central metal ions in the complexes, as well as to the benzene. The calculated charges on metal ions are also reported at various charge schemes. The calculations show encouraging agreement with the available experimental data.
基金Project supported by the National Key Research&Development Program of China(Grant Nos.2016YFA0202300 and 2018YF A0305800)the National Natural Science Foundation of China(Grant Nos.61888102,11604373,61622116,and 51872284)+2 种基金the CAS Pioneer Hundred Talents Program,China,the Strategic Priority Research Program of Chinese Academy of Sciences(Grant Nos.XDB30000000 and XDB28000000)Beijing Nova Program,China(Grant No.Z181100006218023)the University of Chinese Academy of Sciences
文摘A new two-dimensional atomic crystal,monolayer cuprous telluride(Cu2Te)has been fabricated on a grapheneSi C(0001)substrate by molecular beam epitaxy(MBE).The low-energy electron diffraction(LEED)characterization shows that the monolayer Cu2Te forms a √3×√3superstructure with respect to the graphene substrate.The atomic structure of the monolayer Cu2Te is investigated through a combination of scanning tunneling microscopy(STM)experiments and density functional theory(DFT)calculations.The stoichiometry of the Cu2Te sample is verified by x-ray photoelectron spectroscopy(XPS)measurement.The angle-resolved photoemission spectroscopy(ARPES)data present the electronic band structure of the sample,which is in good agreement with the calculated results.Furthermore,air-exposure experiments reveal the chemical stability of the monolayer Cu2Te.The fabrication of this new 2D material with a particular structure may bring new physical properties for future applications.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 10576030 and 10576016) National 973 Project (Grant No. 61337)
文摘Density functional theory (DFT) method has been employed to study the effect of nitroamino group as a substituent in cyclopentane and cyclohexane, which usually construct the polycyclic or caged nitra-mines. Molecular structures were investigated at the B3LYP/6-31G** level, and isodesmic reactions were designed for calculating the group interactions. The results show that the group interactions ac-cord with the group additivity, increasing with the increasing number of nitroamino groups. The dis-tance between substituents influences the interactions. Detonation performances were evaluated by the Kamlet-Jacobs equations based on the predicted densities and heats of formation, while thermal stability and pyrolysis mechanism were studied by the computations of bond dissociation energy (BDE). It is found that the contributions of nitroamino groups to the detonation heat, detonation velocity, detonation pressure, and stability all deviate from the group additivity. Only 3a, 3b, and 9a-9c may be novel potential candidates of high energy density materials (HEDMs) according to the quantitative cri-teria of HEDM (ρ≈ 1.9 g/cm3, D ≈ 9.0 km/s, P ≈ 40.0 GPa). Stability decreases with the increasing number of N-NO2 groups, and homolysis of N-NO2 bond is the initial step in the thermolysis of the title com-pounds. Coupled with the demand of thermal stability (BDE > 20 kcal/mol), only 1,2,4-trinitrotriazacy-clohexane and 1,2,4,5-tetranitrotetraazacyclohexane are suggested as feasible energetic materials. These results may provide basic information for the molecular design of HEDMs.
文摘Based on the octadecahedron of eleven-vertex closo-borane, the eleven-vertex closo-heteroborane was suggested with nonmetallic atoms instead of the different nonequivalent boron, and the stabilities were predicted at G96PW91/6-31＋G（3d,2p） level. The small heteroatoms, C, N, O, preferentially occupy vertex 2 with the absolutely lowest relative energy to form the high stabilization closo-heteroboranes. They cap four-membered rings to satisfy the geometrical demand of short B--Z bonds. The electron attractions from the vicinal boron atoms make the frameworks shrink. Differently, Si and Ge preferentially substitute for boron at vertex 1 with six tight B--Z bonds and form stabilized molecules. P, As, S, and Se tend to occupy vertex 4 and the optimized structures belong to the nido configura- tions. In contrast to high electronegative heteroatoms, S and Se transfer less negative charges to framework and the electropositive heteroatoms, Si and Ge transfer more negative charges to framework to form the delocalization structures. The HOMO-LUMO gaps show that most of predicted clusters possess chemical stabilities. The substitutions of heteroatoms for boron atoms in eleven-vertex closo-heteroboranes are consistent with the topological charge stabilization rule proposed by Gimarc.
基金supported by the National Natural Science Foundation of China(No.22271080)the Joint Guidance Project of Heilongjiang Natural Science Foundation(No.LH2023B020).
文摘The construction of stable and efficient materials that emit blue and green light remains a challenge.Among the blue light materials reported,metal-organic framework(MOF)materials are rarely reported as blue phosphors due to their weak luminescence intensity.Based on the construction of CsPbBr_(3)@MOF(CPB@MOF),an innovative idea was proposed to simultaneously enhance the green luminescence of CPB and the blue luminescence of MOF through the interaction between CPB and MOF for the first time.As expected,the blue luminescence from CPB:7%SCN−@0.5%MOF:Eu as well as the green luminescence from 5%CPB:7%SCN−@MOF:Eu was sufficient to construct high-performance light-emitting diode(LED)devices and further excite solar cells to generate stable photoelectric signals.The white LED(WLED)device with excellent color quality(color rendering index(CRI)=96.2)and correlated color temperature(CCT=9688 K)can be constructed by using the obtained blue-emitting CPB:7%SCN-@0.5%MOF:Eu,green-emitting 5%CPB:7%SCN−@MOF:Eu,and red-emitting PPB:30%Mn^(2+).The density functional theory(DFT)theoretical calculation results indicate that the p orbital of Pb plays the major role in the conduction band,and the p orbital of Br plays the major role in the valance band of CPB and CPB:SCN−.While the p orbital of O plays the major role in both the conduction band and valance band of MOF.The heat capacity of CPB and CPB:SCN−separately reaches the Dulong–Petit limit at 200 and 400 K,indicating that the thermal stability of CsPbBr_(3)increases after SCN−doping.
基金supported by the National Natural Science Foundation of China (Grant No.60877017)the Innovation Program of Shanghai Municipal Education Commission (Grant No.08YZ04)
文摘A plane wave density functional theory method was used to investigate the adsorption properties of isolated alkali metal atoms, including Li, Na, K, Rb and Cs on-top of the F 0 s defective center of MgO（001） surface. Among all the alkali metals, the lithium atom binds most strongly with the highest adsorption energy of 0.67 eV and the shortest distance of about 0.257 nm between metal and the surface, the binding energy for the sodium atom comes second, and just half of this value for the other alkali metal atoms. The relatively strong interaction of Li with the F 0 s center can be explained by a more covalent bonding involved, evidenced by results of both the projected density of states and the projected charge density. The bonding mechanism is discussed in detail.
