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. Author manuscript; available in PMC: 2017 Jun 20.
Published in final edited form as: Inorg Chem. 2016 Jun 8;55(12):5862–5870. doi: 10.1021/acs.inorgchem.6b00148

Table 3.

CASSCF analysis of D

Excitation Energy (cm−1) Dxx (cm−1) Dyy (cm−1) Dzz (cm−1) Directiond D d (cm−1) E/D d
xy→xz 1,038 (2,720)a 2.14 2.68 −4.82 z (x) −7.22 0.04
xy→yz 2,201 (3,496) −2.98 2.03 0.95 x (y) −4.47 0.12
xy→z2 6,506 (8,739) −0.31 0.18 0.13 x (none) −0.47 0.06
xy→x2-y2 9,275 (13,334) 1.21 0.08 −1.29 z (z) −1.94 0.29
Totalb 0.06 4.97 −5.03 z −7.55 0.33
Totalc 0.53 5.13 −5.66 z −8.50 0.27
a

In parentheses: TD-DFT excitation energies obtained with B3LYP/6-311G. (Shown in Figure S7.)

b

Sums of Dii for lowest four transitions, all spin S = 2 conserving, listed in table, and implied D and E/D. The principal axes of the four contributions are assumed to be collinear.

c

Final totals including all S = 0, 1, 2 contributions.

d

Rows 1–4 list the D and E/D values associated with levels at Δdi such that E/D is confined to 0 ≤ E/D ≤ 1/3. The direction of the largest component of Dii is given in the 6th column. In parentheses: the direction predicted by the model of Figure 6 with the commonly used spin–orbit coupling operator for the transition indicated.