权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Electron and spin transfer theory based on the time-dependent variational principle

基于瞬态变分原理的电子和自旋转移理论

基本信息

批准号：
13640496
负责人：
OHTA Katsuhisa
金额：
$ 1.41万
依托单位：
MURORAN INSTITUTE OF TECHNOLOGY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

项目摘要

Time-dependent variational principle (TDVP) under inequality constraints with general physical quantity expectation values has been investigated to apply for the time-development of many-electron wavefunctions in the electron- and spin-transfer processes in molecules. The Hilbert subspace in which the inequality constraints are satisfied is defined as phase-I. The subspace in which the equality constraints are active is defined as phase-II. The total action for the TDVP is defined with the direct sum of actions in subspaces. Weierstrass-Erdmann's corner condition is also considered.The spin-unrestricted Hartree-Fock (UHF) wavefunctions are often adopted as initial states of spin- and electron-transfer processes. The unpaired orbitals in the UHF wavefunctions take an important role in the transfer processes. We have investigated a handy way to find radical orbitals buried in UHF wavefunctions and the variational meaning of Koopmans' theorem. For doublet radicals, the highest occupied molecular orbital (HOMO) of α-orbitals usually corresponds to the radical orbital which is occupied by an unpaired electron. Occasionally, however, the α-HOMO fails to identify the radical orbital while the lowest unoccupied MO (LUMO) of β-orbitals indicates the radical orbital correctly. In this work, we have examined the applicability of the handy way to identify the radical orbital with the α -HOMO or the β -LUMO of UHF wavefunctions. Koopmans' theorem not only provides a numerical method to calculate approximate ionization potential energies but also has another variational meaning. We have shown that an extension of the variational meaning of the theorem to many-electron ionization processes leads naturally to the SCF equation for hole orbitals.

本文研究了不等式约束下含时变分原理（TDVP）在一般物理量期望值下对分子中电子和自旋转移过程中多电子波函数的时间展开的应用。定义满足不等式约束的Hilbert子空间为相I。其中等式约束是活跃的子空间被定义为阶段II。TDVP的总作用量定义为子空间中作用量的直和。我们还考虑了Weierstrass-Erdmann角点条件，自旋非限制的Hartree-Fock（UHF）波函数常被用作自旋和电子转移过程的初始态。UHF波函数中的不成对轨道在传输过程中起着重要的作用。本文研究了一种寻找UHF波函数中根轨道的简便方法和Koopmans定理的变分意义。对于二重态自由基，α轨道的最高占据分子轨道（HOMO）通常对应于被未成对电子占据的自由基轨道，但有时α-HOMO不能识别自由基轨道，而β轨道的最低未占据分子轨道（LUMO）则能正确识别自由基轨道。本文研究了用UHF波函数的α -HOMO或β -LUMO识别自由基轨道的简便方法的适用性。Koopmans定理不仅提供了一种计算近似电离势能的数值方法，而且具有另一种变分意义。我们已经表明，延伸的变分意义的定理，多电子电离过程自然导致SCF方程的空穴轨道。