低自旋d~5络合物的ESR参数计算方法及其数学模型

低自旋d~5络合物ESR参数计算结果证明,最低Kramers简并态,不仅其自旋——轨函与能量矩阵中基函符号一致,而且叩l±能够直接满足Kramers简并态相位关系即(Ψ_1~+)=iΨ_1~-,或者(Ψ_1~-)·=-iΨ_1~+。使用Ψ_1~±推导低自旋d~5络合物的g张量主值表达式时亦不必改变g_(yy)和g_(xx)表达式的符号即直接满足计算条件g_(zz)>g_(yy)>g_(xx)>0。本文提出四十八种g值和符号组合,以及四个定性判据;同时提出并应用实轨函与复轨函的系数关系式证明了实轨函法与复轨函法配位场参数表达式的一致性。

The Calculation Methods of ESR Parameters of Low-Spin d~5 Complexes——Rationalities of Mathematical Model and Calculation Methods

Results of ESR parameter calculation of low-spin d5 complexes indicate that Kramers doublets n+= satisfy phase relationship,i. e. , and the principal g-tensor value expressionsderived by using have been found to satisfy directly the combinations of g-values and signs 1gzz|>|gyy>1gxx| and( + + + ) without change of signs of gyy and gxx expressions.48 combinations of g-values and signs are proposed in this paper, and four qualitative criterions are put forward based on physical and structural factors to examine the parameters which condition each other.By using the relational expressions proposed in this paper between the real orbital and the complex orbital coefficients the consistency of the real orbital and the complex orbital methods has been proved in calculation of ligand-field parameters of low-spin d5 complexes.