Table 4 EDA-NOCV results for doublet [M(N₂)₈]⁺ (M = Ca, Sr, Ba) complexes at the M06-2X/TZ2P-ZORA//M06-2X-D3/def2-TZVPP level

∆E_int

−106.7

−100.3

−74.3

∆E_hybrid

27.0

27.0

17.2

∆E_Pauli

38.3

38.6

48.6

∆E_elstat^a

−48.3 (28.1%)

−45.7 (27.5%)

−49.3 (35.2%)

∆E_orb^a

−123.7 (71.9%)

−120.2 (72.5%)

−90.9 (64.8%)

∆E_orb(1)^b

[M(d)]⁺→(N₂)₈ π backdonation

−49.9 (40.3%)

−55.7 (46.3%)

−36.0 (39.6%)

∆E_orb(2)^b

[M(d)]⁺←(N₂)₈ σ donation

−17.4 (14.1%)

−16.2 (13.5%)

−14.6 (16.1%)

∆E_orb(3)^b

[M(d)]⁺←(N₂)₈ σ donation

−13.6 (11.0%)

−11.2 (9.3%)

−6.2 (6.8%)

∆E_orb(4)^b

[M(s)]⁺←(N₂)₈ σ donation

−6.4 (5.2%)

−6.0 (5.0%)

−4.4 (4.8%)

∆E_orb(5)^b

[M(p)]⁺←(N₂)₈ σ donation

−7.0 (5.7%)

−5.4 (4.5%)

−4.4 (4.8%)

∆E_orb(6)^b

[M(p)]⁺←(N₂)₈ σ donation

−3.0 (2.4%)

−3.5 (2.9%)

−2.2 (2.4%)

∆E_orb(7)^b

(N₂)₈ polarization

–c–

–c–

−2.5 (2.8%)

∆E_orb(rest)

−26.4 (21.3%)

−22.2 (18.5%)

−20.6 (22.7%)