理论研究V2O6-的结构和电子性质

The geometrical and electronic properties of the anionic and neutral V2O6 clusters were studied with the spin unrestricted hybrid density functional B3LYP method. The calculated ground states of both clusters are different from the previous theoretical results. The ground state of V2O6- is found to be a doublet with C2v symmetry, while a doublet with D2h symmetry was previously obtained by Vyboishchikov and Sauer. For neutral V2O6, the ground state is an open-shell singlet with D2h symmetry whose energy is very close to that of the triplet state. In contrast, a closed-shell singlet with D2h symmetry was obtained by Vyboishchikov and Sauer, and Calatayud et al. found a triplet ground state with Cs symmetry. Moreover,the calculated adiabatic and vertical detachment energies of the anion cluster are in much better agreement with the experimental results of photoelectron spectroscopy than previous theoretical values.     

多组态含时自旋非限制HartreeFock理论

基于自旋非限制HartreeFock理论,发展了自旋非限制多组态含时HartreeFock理论方法来研究激光场中的多电子相关动力学．自旋向上和自旋向下的自旋轨道分别在他们各自的子空间内传播;并通过约化密度矩阵和平均场算符相互作用．分别利用了自旋限制和非限制的多组态含时HartreeFock方法虚时和实时传播计算氦原子基态能量和电离几率．自旋非限制的计算结果与其他报道相吻合．     

理论研究V2O6-的结构和电子性质

采用自旋非限制密度泛函(B3LYP)方法研究了V2O6-的结构和电子性质,得到的基态和前人的理论计算结果不同．V2O6-阴离子是具有C2v对称性的双重基态,而以前Vyboishchikov等人得到的结果为D2h对称性双重基态．V2O6中性分了是具有D2h对称性的开壳层单重基态,它的能量和三重态的非常接近,而Vyboishchikov等人和Calatayud等人分别得到D2h对称性的闭壳层单重基态和Cs对称性的三重基态．从该基态结果出发计算出的电子分离能和实验上的PES谱相符,相反前人得到的电子分离能和实验相差较大．     

Electronic and spectral properties of ametal-organic super container molecule by single point DFT

ABSTRACT

Metal-organic super container (MOSC) molecules are ideal candidates for photocatalysis due to their construction with transition metal centres and tuneable cavity sizes that could house catalytic sites. The basic electronic structure for a model of extremely large size (more than 2000 ions) is explored by single point calculation using unrestricted density functional theory, and Perdue–Burke–Ernzerhof functional in Vienna ab initio simulation package software. The information obtained through these calculations (such as density of states, absorbance spectra, and charge density) will allow for analysis of a MOSC's catalytic ability. Electronic characteristics of the nanostructures (MOSCs and their building blocks) in the ground and photoexcited electronic configurations are examined. We explore if the presence of transition metal ions with open shells in such close proximity to one another may result in high spin configurations and show any arrangement into ferromagnetic ordering. Spin-unrestricted computation was applied to evaluate how optical properties could be affected by d–d transitions. A scan of a spin-polarisation parameter allows one to resolve spin configuration and obtain a connection between theory and experiment. Analysis of Kohn–Sham orbitals of interest provides insight into charge transfer mechanisms, which were found to contribute to multiple low-energy charge transfer states to the electronic structure.     

多组态含时自旋非限制Hartree Fock理论 (cited: 1)

基于自旋非限制Hartree Fock理论,发展了自旋非限制多组态含时Hartree Fock理论方法来研究激光场中的多电子相关动力学．自旋向上和自旋向下的自旋轨道分别在他们各自的子空间内传播;并通过约化密度矩阵和平均场算符相互作用．分别利用了自旋限制和非限制的多组态含时Hartree Fock方法虚时和实时传播计算氦原子基态能量和电离几率．自旋非限制的计算结果与其他报道相合．