Table 10. Bond Dissociation Energies for Removing All Ligands from the Complex at 0 K, Excluding ZPE (Deviation from B3LYP/aug-cc-pVTZ for Our Mixed-Ligand Test Set).

	Bond Dissociation Energy (kcal/mol)
	B3LYPa	B97-1a	B3LYPb	PBEb	DFTB3	B3LYPa//DFTB3c
[Cu(OH)(H2O) (NH3)2]+	594.6	–1.1	+11.3	+35.5	+3.0	–1.0
[Cu(H2O) (NH3)4]2+	383.8	+0.3	+13.2	+37.6	–16.1	–0.1
[Cu(H2O)2(NH3)2]2+	340.6	–1.8	+10.5	+31.0	–14.1	–0.0
[Cu(H2O)2(NH3)4]2+	398.8	+1.5	+15.2	+41.0	–11.3	–1.0
[Cu(OH) (NH3)3]+	601.3	–0.7	+11.4	+36.4	–0.6	–0.8
[Cu(OH) (NH3)4]+	613.9	+0.7	+13.1	+39.1	+0.7	–1.5
[Cu(SH) (NH3)3]+	572.6	–0.9	+9.6	+38.0	–9.9	–0.4
[Cu(SH) (NH3)4]+	582.9	+1.2	+11.3	+41.1	–6.8	–1.9
[Cu(SH2) (NH3)4]2+	377.5	+1.1	+12.5	+38.9	–15.5	–1.5
[Cu(SH) (SH2) (NH3)2]+	561.2	–0.6	+8.6	+40.2	–7.5	–1.1
[Cu(SH2)2(H2O) (NH3)]2+	321.8	–0.8	+8.4	+35.8	–8.7	–2.1
[Cu(SH2)2(H2O) (NH3)2]2+	355.7	+0.7	+10.9	+39.2	–8.9	–1.1
[Cu(SH2)2(H2O)2(NH3)2]2+	370.0	+2.1	+13.2	+42.1	–3.1	–0.6
[Cu(SH2)2(H2O)2]2+	307.5	–1.5	+8.0	+34.0	–5.0	–2.0
[Cu(SH2)2(H2O)3]2+	330.2	–0.5	+10.1	+36.1	–2.7	–2.4
[Cu(SH2)2(H2O)4]2+	345.3	+0.9	+12.7	+37.7	+2.0	–0.8
[Cu(SH2)2(NH3)2]2+	336.1	–0.3	+8.7	+37.3	–13.3	–1.4
[Cu(SH2)3(NH3)2]2+	351.3	+1.4	+9.9	+41.0	–9.2	–1.9
[Cu(SH2)4(H2O)]2+	324.7	+1.8	+8.6	+41.9	–1.4	–3.0
[Cu(SH2)4(H2O)2]2+	337.8	+3.2	+11.0	+44.3	+5.9	–2.3
[Cu(SH2)2(H2O) (NH3)]+	119.3	+2.0	+7.1	+23.8	+1.8	–1.2
[Cu(SH2)2(H2O)2]+	110.5	+1.5	+6.9	+22.0	+2.1	–4.2
[Cu(SH2)2(NH3)2]+	125.1	+2.1	+7.0	+24.4	+7.1	–4.2
MAD		1.2	10.4	36.5	6.8	1.6
MAX		3.2	15.2	44.3	16.1	4.2

^aaug-cc-pVTZ.

^b6-31+G(d,p).

^cB3LYP single-point calculations on top of DFTB3 geometries.