. Author manuscript; available in PMC: 2017 Aug 21.

Published in final edited form as: Phys Chem Chem Phys. 2016 Apr 20;18(31):21162–21171. doi: 10.1039/c6cp00349d

Table 1.

PW91-D3 and OLYP-D3 Calculated Properties for the Optimized Geometries of Fe³⁺-(O-OH)⁻-Cu²⁺-Y237⁻ and Fe³⁺-(HO-O)⁻-Cu²⁺-Y237⁻ DNC Models with or without the “Extra” Proton on His376.^a

State	Geometry				E	Q	pK_a (H376)	Net Spin
State	Fe-O1	O1-O2	Cu-O2	Fe···Cu	E	Q	pK_a (H376)	Fe_a3	Cu_B	O1	O2	Y237
PW91-D3:
Fe³⁺-(O-OH)⁻-Cu²⁺-Y237⁻-H376	1.78	1.53	2.08	4.36	2.2	0		0.81	−0.37	0.15	−0.06	−0.33
Fe³⁺-(O-OH)⁻-Cu²⁺-Y237⁻-H376⁺	1.78	1.53	2.10	4.38	0.0	1	11.2	0.81	−0.37	0.15	−0.06	−0.34
Fe³⁺-(HO-O)⁻-Cu²⁺-Y237⁻-H376	2.01	1.46	1.94	4.30	13.6	0		0.74	−0.47	−0.01	−0.19	0.09
Fe³⁺-(HO-O)⁻-Cu²⁺-Y237⁻-H376⁺	2.00	1.47	1.94	4.31	10.8	1	11.7	0.84	−0.41	0.00	−0.14	−0.15
OLYP-D3:
Fe³⁺-(O-OH)⁻-Cu²⁺-Y237⁻-H376	1.80	1.48	2.37	4.71	0.3	0		0.89	−0.30	0.15	−0.03	−0.52
Fe³⁺-(O-OH)⁻-Cu²⁺-Y237⁻-H376⁺	1.79	1.49	2.32	4.67	0.0	1	11.0	0.89	−0.30	0.15	−0.03	−0.52
Fe³⁺-(HO-O)⁻-Cu²⁺-Y237⁻-H376	2.09	1.44	1.97	4.47	12.7	0		0.78	−0.44	−0.03	−0.25	0.12
Fe³⁺-(HO-O)⁻-Cu²⁺-Y237⁻-H376⁺	2.08	1.45	1.98	4.50	11.8	1	11.5	0.91	−0.37	−0.01	−0.17	−0.22

The calculated properties include geometries (Å), energies (E, offset by −29320.2 kcal mol⁻¹ and −28044.7 kcal mol⁻¹, respectively, in PW91-D3 and OLYP-D3 calculations), the total charge (Q) of the model cluster, the pK_a values of the His376 side chain, and the Mulliken net spin populations on Fe_a3, Cu_B, O1, O2, and on the heavy atoms of the Tyr237 side chain (the sum total).