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关于如何统一解释立方d~5络合物的EPR(Electron paramagnetic resonance,电子顺磁共振)参量(零场分裂参量a和g张量)与光谱的问题,自1934年van Vleck和Penney提出以后,长期得不到解决.直到1990年前后,邝和周等才给出了统一计算参量a和光谱的两种不同的方法,但未解决g张量的计算问题.d~5离子的g张量计算比其它d~n(n≠5)离子困难得多,是因为基态~6S为轨道单态,不会被任何晶体场分裂,以致通常的g张量公式不能采用.最近周和杨发展了一种单行列式基函(SDB)EPR理论方法,给出了有效自旋为1/2的d~5离子的g张量公式.但大多数情况下d~5离子的有效自旋为5/2,所以上述SDB方法尚待完善.本文在周等工作的基础上导出普遍适用的立方场d~5离子g张量公式,并对d~5络合物Mn~(2+):CaF_2和Mn~(2+):KZnF_3的零场分裂参量a、g张量和光谱进行统一计算,作出统一解释.值得指出的是,周等方法的基础是在自旋-轨道耦合空间的SГβГ’γ’表象内将d电子间静电相互作用(?)_(ee)(B,C)、晶场作用能(?)_c(D_q)和自旋-轨道相互作用(?)_(so)(ξ)同时(而不是逐次)对角化,这不同于流行的弱场耦合、强场耦合和中等场耦合等逐次对角化图象,而是一种统一晶场耦合图象(Unified crystal-field coupling scheme,缩写为UCFC图象).由于这种图象不需?
On how to unify the EPR (Electron paramagnetic resonance) parameters (zero field splitting parameters a and g tensors) and spectra of cubic d5 complex, since 1934 when van Vleck and Penney proposed, Until 1990. Before and after 1990, Kwong and Zhou gave two different methods to unify the calculation of the parameter a and the spectrum, but did not solve the problem of calculating the g-tensor. The other d ~ n (n ≠ 5) ions are much more difficult because the ground state ~ 6S is singular orbit and will not be split by any crystal field, so that the usual g-tensor formula can not be used. Recently, The single-column basis function (SDB) EPR theory gives the g-tensor formula of d ~ 5 ions whose effective spin is 1/2, but in most cases the effective spin of d ~ 5 ions is 5/2 , So the above SDB method is still to be perfected.This paper deduces the universally applicable cubic tensor d5 ion g-tensor formula on the basis of week work, and studies the d ~ 5 complex Mn2 +: CaF2 and Mn ~ (2 +): KZnF_3 zero-field splitting parameters a, g tensors and spectra unified calculation to make a unified explanation.It is worth noting that the basis of the weekly method is the spin-orbit In the SГβГ’γ ’image of the coupling space, the interaction between the d electrons (?) Ee (B, C), the interaction between the crystal field (?) C and the spin-orbit interaction ) _ (so) (ξ) diagonally at the same time rather than sequentially, which is different from the popular sequential diagonalization of weak field coupling, strong field coupling and medium field coupling, but a uniform crystal field coupling Image (Unified crystal-field coupling scheme, abbreviated as UCFC image). Since this image does not need?