Table 4 Calculated relative electronic energies E and g-values with different point groups for the [Cr(CO)6]•+ cationa

From: Stable salts of the hexacarbonyl chromium(I) cation and its pentacarbonyl-nitrosyl chromium(I) analogue

 

Exp.

D 3d

C 2h

D 4h

D 2h b

O h c

ΔE

 

0 (0.00)

26 (0.31)

136 (1.63)

71 (0.85)

410 (4.92)

\(g_ \bot\)

2.185

2.173

2.177

2.434

  

\(g_\parallel\)

1.947

1.971

1.969

1.761

  

g iso d

2.106

2.106

2.108

2.210

  
  1. aElectronic energies were calculated with DLPNO-CCSD(T)/def2-TZVPP (E in cm−1; kJ  mol−1 in parentheses), structures were optimized with TPSSh-D3BJ/def2-TZVPP; the calculated (NEVPT2-SA-CAS-SCF/cc-pVTZ) anisotropic g-tensor components perpendicular (\(g_ \bot\)) and parallel (\(g_\parallel\)) to the principal molecular axis as well as isotropic g-values for the minimum structures D3d, C2h and D4h are compared to the experimental values (exp.)
  2. bTransition state structure connecting two equivalent D3d symmetric structures
  3. cNot a stationary point
  4. dgiso  =  (2*g⊥  +  g∥)/3
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