Vanadium dioxide VO_(2) is a strongly correlated material that undergoes a metal-to-insulator transition around 340 K.In order to describe the electron correlation effects in VO_(2), the DFT+U method is commonly emplo...Vanadium dioxide VO_(2) is a strongly correlated material that undergoes a metal-to-insulator transition around 340 K.In order to describe the electron correlation effects in VO_(2), the DFT+U method is commonly employed in calculations.However, the choice of the Hubbard U parameter has been a subject of debate and its value has been reported over a wide range. In this paper, taking focus on the phase transition behavior of VO_(2), the Hubbard U parameter for vanadium oxide is determined by using the quasi-harmonic approximation(QHA). First-principles calculations demonstrate that the phase transition temperature can be modulated by varying the U values. The phase transition temperature can be well reproduced by the calculations using the Perdew–Burke–Ernzerhof functional combined with the U parameter of 1.5eV. Additionally,the calculated band structure, insulating or metallic properties, and phonon dispersion with this U value are in line with experimental observations. By employing the QHA to determine the Hubbard U parameter, this study provides valuable insights into the phase transition behavior of VO_(2). The findings highlight the importance of electron correlation effects in accurately describing the properties of this material. The agreement between the calculated results and experimental observations further validates the chosen U value and supports the use of the DFT+U method in studying VO_(2).展开更多
The formation and migration of polarons have important influences on physical and chemical properties of transition metal oxides.Density functional theory plus the Hubbard U correction(DFT+U)and constrained density fu...The formation and migration of polarons have important influences on physical and chemical properties of transition metal oxides.Density functional theory plus the Hubbard U correction(DFT+U)and constrained density functional theory(cDFT)are often used to obtain the transfer properties for small polarons.In this work we have implemented the cDFT plus the Hubbard U correction method in the projector augmented wave(PAW)framework,andapplied it to study polaron transfer in the bulk phases of TiO_(2).We have confirmed that the parameter U can have significant impact on theoretical prediction of polaronic properties.It was found that using the Hubbard U calculated by the cDFT method with the same orbital projection as used in DFT+U,one can obtain theoretical prediction of polaronic properties of rutile and anatase phases of TiO_(2) in good agreement with experiment.This work indicates that the cDFT+U method with consistently evaluated U is a promising first-principles approach to polaronic properties of transition metal oxides without empirical input.展开更多
In the equation U = I – A for the Mott energy, the electron-hole interaction of the successor state is missing. Adding the attractive term, the energy for disproportionation (Hubbard U), may adopt any sign. The missi...In the equation U = I – A for the Mott energy, the electron-hole interaction of the successor state is missing. Adding the attractive term, the energy for disproportionation (Hubbard U), may adopt any sign. The missing term is related to the Born effect, the Madelung correction and the Lattice Enthalpy.展开更多
Advanced GGA ＋ U（Hubbard） and modified Becke–Johnson（mBJ） techniques are used for the calculation of the structural, electronic, and optical parameters of α-Al2-x CoxO3（x = 0.0, 0.167） compounds. The direct b...Advanced GGA ＋ U（Hubbard） and modified Becke–Johnson（mBJ） techniques are used for the calculation of the structural, electronic, and optical parameters of α-Al2-x CoxO3（x = 0.0, 0.167） compounds. The direct band gaps calculated by GGA and m BJ for pure alumina are 6.3 eV and 8.5 eV, respectively. The m BJ approximation provides results very close to the experimental one（8.7 eV）. The substitution of Al with Co reduces the band gap of alumina. The wide and direct band gap of the doped alumina predicts that it can efficiently be used in optoelectronic devices. The optical properties of the compounds like dielectric functions and energy loss function are also calculated. The rhombohedral structure of theα-Al2-x CoxO3（x = 0.0, 0.167） compounds reveal the birefringence properties.展开更多
本文采用第一性原理的方法系统研究了UO2的晶体结构、电子结构和弹性性质.在计算中采用广义梯度近似结合Hubbard U项描述电子的局域强关联效应.首先通过计算能带带隙大小并与理论值比较的方法,得到了合理的有效库仑相关作用能(Ueff)的取...本文采用第一性原理的方法系统研究了UO2的晶体结构、电子结构和弹性性质.在计算中采用广义梯度近似结合Hubbard U项描述电子的局域强关联效应.首先通过计算能带带隙大小并与理论值比较的方法,得到了合理的有效库仑相关作用能(Ueff)的取值,同时通过态密度的计算,进一步验证了Ueff取值的合理性.计算得到UO2中U原子的Ueff值为3.30 e V(Ueff=U-J,U=3.70 e V,J=0.40 e V).应用此参数计算得到的UO2晶格常数为5.54,带隙宽度为2.17 e V.该结果优于目前现有的研究结果,同时在同样的Ueff值条件下计算所得到的弹性常数与实验值也符合得较好.相较于之前的基于实验测量并分析得到的Ueff值,我们所采用的方法在对UO2性质描述上更为准确.不同的有效库仑相关作用能取值下的态密度结果表明,有效库仑相关作用能的大小可以影响铀原子5f电子轨道的分布.展开更多
基金supported by the National Natural Science Foundation of China (Grant Nos.21933006 and 21773124)the Fundamental Research Funds for the Central Universities Nankai University (Grant Nos.010-63233001,63221346,63213042,and ZB22000103)+1 种基金the support from the China Postdoctoral Science Foundation (Grant No.2021M691674)the Hefei National Laboratory for Physical Sciences at the Microscale (Grant No.KF2020105)。
文摘Vanadium dioxide VO_(2) is a strongly correlated material that undergoes a metal-to-insulator transition around 340 K.In order to describe the electron correlation effects in VO_(2), the DFT+U method is commonly employed in calculations.However, the choice of the Hubbard U parameter has been a subject of debate and its value has been reported over a wide range. In this paper, taking focus on the phase transition behavior of VO_(2), the Hubbard U parameter for vanadium oxide is determined by using the quasi-harmonic approximation(QHA). First-principles calculations demonstrate that the phase transition temperature can be modulated by varying the U values. The phase transition temperature can be well reproduced by the calculations using the Perdew–Burke–Ernzerhof functional combined with the U parameter of 1.5eV. Additionally,the calculated band structure, insulating or metallic properties, and phonon dispersion with this U value are in line with experimental observations. By employing the QHA to determine the Hubbard U parameter, this study provides valuable insights into the phase transition behavior of VO_(2). The findings highlight the importance of electron correlation effects in accurately describing the properties of this material. The agreement between the calculated results and experimental observations further validates the chosen U value and supports the use of the DFT+U method in studying VO_(2).
基金supported by the National Natural Science Foundation of China (No.21873005 and No.21911530231)High-Performance Computing Platform of Peking University
文摘The formation and migration of polarons have important influences on physical and chemical properties of transition metal oxides.Density functional theory plus the Hubbard U correction(DFT+U)and constrained density functional theory(cDFT)are often used to obtain the transfer properties for small polarons.In this work we have implemented the cDFT plus the Hubbard U correction method in the projector augmented wave(PAW)framework,andapplied it to study polaron transfer in the bulk phases of TiO_(2).We have confirmed that the parameter U can have significant impact on theoretical prediction of polaronic properties.It was found that using the Hubbard U calculated by the cDFT method with the same orbital projection as used in DFT+U,one can obtain theoretical prediction of polaronic properties of rutile and anatase phases of TiO_(2) in good agreement with experiment.This work indicates that the cDFT+U method with consistently evaluated U is a promising first-principles approach to polaronic properties of transition metal oxides without empirical input.
文摘In the equation U = I – A for the Mott energy, the electron-hole interaction of the successor state is missing. Adding the attractive term, the energy for disproportionation (Hubbard U), may adopt any sign. The missing term is related to the Born effect, the Madelung correction and the Lattice Enthalpy.
文摘Advanced GGA ＋ U（Hubbard） and modified Becke–Johnson（mBJ） techniques are used for the calculation of the structural, electronic, and optical parameters of α-Al2-x CoxO3（x = 0.0, 0.167） compounds. The direct band gaps calculated by GGA and m BJ for pure alumina are 6.3 eV and 8.5 eV, respectively. The m BJ approximation provides results very close to the experimental one（8.7 eV）. The substitution of Al with Co reduces the band gap of alumina. The wide and direct band gap of the doped alumina predicts that it can efficiently be used in optoelectronic devices. The optical properties of the compounds like dielectric functions and energy loss function are also calculated. The rhombohedral structure of theα-Al2-x CoxO3（x = 0.0, 0.167） compounds reveal the birefringence properties.
文摘本文采用第一性原理的方法系统研究了UO2的晶体结构、电子结构和弹性性质.在计算中采用广义梯度近似结合Hubbard U项描述电子的局域强关联效应.首先通过计算能带带隙大小并与理论值比较的方法,得到了合理的有效库仑相关作用能(Ueff)的取值,同时通过态密度的计算,进一步验证了Ueff取值的合理性.计算得到UO2中U原子的Ueff值为3.30 e V(Ueff=U-J,U=3.70 e V,J=0.40 e V).应用此参数计算得到的UO2晶格常数为5.54,带隙宽度为2.17 e V.该结果优于目前现有的研究结果,同时在同样的Ueff值条件下计算所得到的弹性常数与实验值也符合得较好.相较于之前的基于实验测量并分析得到的Ueff值,我们所采用的方法在对UO2性质描述上更为准确.不同的有效库仑相关作用能取值下的态密度结果表明,有效库仑相关作用能的大小可以影响铀原子5f电子轨道的分布.
