. Author manuscript; available in PMC: 2008 Aug 17.

Published in final edited form as: J Am Chem Soc. 2007 Feb 28;129(11):3135–3147. doi: 10.1021/ja0654074

Table 5.

Detailed breakdown of the QM/MM//UDFT free energies (at 298 K) relative to the reduced state of putative intermediates for the activation of dioxygen reaction proposed based on QM/MM//RDFT results.^e

Model	H_Red	H_Superoxo (11)	H_Superoxo (3)	H_Superoxo (1)	H_Peroxo Aμ-1,2 (1)	H_Peroxo μ,η²,η¹ (1)	H_Peroxo μ,η²,η² (1)	H_Q (1)
ΔE_QM/MM-UDFT	0	4.64	1.72	5.65	−3.40	−6.28	−9.27	−8.86
ΔZPE	0	−3.5	−3.66	−2.71	−3.38	2.95	−2.75	−2.37
ΔΔH_Corrections	0	0.21	0.81	−0.09	1.17	0.23	−0.22	−0.22
ΔS	0	−4.68	0.54	−12.21	2.26	−8.98	−13.25	−16.02
−TΔS	0	1.39	−0.16	3.64	−0.67	2.68	3.95	4.78
Spin-projection Corrections	-	-	-	-	−0.08	−0.04	−0.90	−1.76

ΔH	0	1.35	−1.13	2.85	−5.69	−3.14	−13.14	−13.21
ΔG	0	2.74	−1.29	6.49	−6.36	−0.46	−9.19	−8.43