Table 1.

Experimental and Calculated Vertical Ionization Energies (eV) and Oxidation Potentials (V versus Fc/Fc⁺).

Molecule	Expt. IEv	Calc. IEv	Er+	ΔGsolv	ΔG (trans, rot, vib)	Calc. $E_{\mathit{\text{ox}}}^{\mathrm{o}}$	Expt. $E_{\mathit{\text{ox}}}^{\mathrm{o}}$
alkoxide ligands
A	6.63	6.66	0.50	0.86	0.04	0.09	0.09
B	6.60	6.54	0.48	0.85	0.02	0.02	0.05
C	6.58	6.52	0.51	0.81	0.06	−0.03	0.03
diolato ligands
D	6.84	6.71	0.15	0.85	0.01	0.54	0.44
E	6.81	6.61	0.17	0.83	0.01	0.44	0.47
F	6.71	6.58	0.20	0.85	0.02	0.36	0.32

IE_v is the gas-phase vertical ionization energy (eV). The experimental IE_v values were obtained by fitting the spectroscopic data and have an uncertainty of ±0.02 eV. E_r⁺ is the calculated gas-phase reorganization energy of the molecular positive ion (eV). ΔG_solv is the calculated difference in free energy of solvation of the molecular cation and neutral species in dichloromethane (G_s⁺ − G_s^o, eV). ΔG_{trans,rot,vib} is the calculated gas-phase translational, rotational, and vibrational contributions to the free energy change with ionization (eV). $E_{\mathit{\text{ox}}}^{\mathrm{o}}$ is the standard oxidation potential in V versus Fc/Fc⁺ with a ±5 mV uncertainty.