. 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 2.

PW91-D3 and OLYP-D3 Calculated Properties for the Optimized Geometries of Fe⁴⁺=O²⁻…OH⁻-Cu²⁺-Y237^• and Fe⁴⁺=O²⁻···HO⁻-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:
Fe⁴⁺=O²⁻…OH⁻-Cu²⁺-Y237^•-H376	1.65	2.79	1.89	4.59	−0.1	0		1.11	−0.50	0.78	−0.32	−0.71
Fe⁴⁺=O²⁻…OH⁻-Cu²⁺-Y237^•-H376⁺	1.65	2.75	1.89	4.54	−3.9	1	12.4	1.11	−0.50	0.78	−0.32	−0.71
Fe⁴⁺=O²⁻···HO⁻-Cu²⁺-Y237^•-H376	1.66	2.64	1.91	4.52	−14.8	0		1.25	−0.52	0.75	−0.17	−0.89
Fe⁴⁺=O²⁻···HO⁻-Cu²⁺-Y237^•-H376⁺	1.66	2.64	1.91	4.55	−17.7	1	11.8	1.25	−0.52	0.75	−0.17	−0.89

OLYP-D3:
Fe⁴⁺=O²⁻…OH⁻-Cu²⁺-Y237^•-H376	1.64	3.06	1.89	4.99	−10.6	0		1.17	−0.48	0.87	−0.31	−0.87
Fe⁴⁺=O²⁻…OH⁻-Cu²⁺-Y237^•-H376⁺	1.65	3.14	1.89	5.09	−12.0	1	11.8	1.17	−0.48	0.88	−0.30	−0.90
Fe⁴⁺=O²⁻···HO⁻-Cu²⁺-Y237^•-H376	1.65	2.89	1.92	4.95	−17.6	0		1.25	−0.51	0.82	−0.23	−0.93
Fe⁴⁺=O²⁻···HO⁻-Cu²⁺-Y237^•-H376⁺	1.65	2.87	1.93	4.93	−18.9	1	11.8	1.25	−0.51	0.81	−0.23	−0.93

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).