Table 3.

Vertical excitation energies (eV) of the first $n\to {\pi }^{*}$ electronic transition and atomic charges (a.u.) of the complexes shown in Figure 1 at the B3LYP geometry and after optimization.

		(at B3LYP geometry)				Absolute	${\omega }_{n\to \pi *}$
System	Method	q ${}_{HW1}$	qOW	q ${}_{HW2}$	${\omega }_{n\to \pi *}$	error	(after optimization)
Fm	B3LYP				5.6388 (0.0009)
Fm–W	B3LYP	0.303	−0.654	0.327	5.7964 (0.0011)		5.7964 (0.0011)
Fm–W	B3LYP/FQ	0.406	−0.726	0.320	5.8136 (0.0008)	0.0172	5.8129 (0.0009)
Fm–W	B3LYP/FX	0.417	−0.834	0.417	5.8089 (0.0009)	0.0125	5.8733 (0.0009)
Py	B3LYP				4.8358 (0.0043)
Py–W	B3LYP	0.285	−0.694	0.312	5.0330 (0.0033)		5.0330 (0.0033)
Py–W	B3LYP/FQ	0.356	−0.660	0.304	5.0806 (0.0046)	0.0476	5.1378 (0.0047)
Py–W	B3LYP/FX	0.417	−0.834	0.417	5.1188 (0.0046)	0.0858	5.1552 (0.0046)
Pm	B3LYP				4.3090 (0.0053)
Pm–W2	B3LYP	0.291	−0.686	0.318	4.5344 (0.0041)		4.5344 (0.0041)
Pm–W2	B3LYP/FQ	0.338	−0.656	0.318	4.5305 (0.0056)	0.0040	4.5935 (0.0056)
Pm–W2	B3LYP/FX	0.417	−0.834	0.417	4.5947 (0.0056)	0.0602	4.6435 (0.0057)
Ac	B3LYP				4.3978 (0.0000)
Ac–W2	B3LYP	0.290	−0.676	0.321	4.6477 (0.0000)		4.6477 (0.0000)
Ac–W2	B3LYP/FQ	0.387	−0.699	0.312	4.6540 (0.0000)	0.0063	4.6864 (0.0000)
Ac–W2	B3LYP/FX	0.417	−0.834	0.417	4.6619 (0.0000)	0.0142	4.7870 (0.0000)

The 6‐31+G* basis set has been used in all cases. The Mean Absolute Error averaged over the four complexes of B3LYP/FQ (B3LYP/FX) is 0.0188 (0.0432) eV