Optical Properties of DMA-π-DCV Derivatives: A Theoretical Inspection under the DFT Microscope

Table 4

Donor-acceptor distance d (in Å), Λ index, and signed deviations (in eV) of three representative density functionals compared to the absolute experimental values of the low-lying CT electronic transitions (TTF → TCB) and (DMA → TCB).

		Λ	Signed deviation			Experimental CT band (eV)
			BLYP	PBE0	wB97XD
TTF-TCB-H ()	5.19	0.42	−0.64	−0.10	0.59	1.61
TTF-TCB-NMe2 ()	5.20	0.46	−0.54	−0.07	0.59	1.69
TTF-TCB-NMe2 ()	6.06	0.62	−0.05	0.29	0.56	2.64

The donor-acceptor distance (in Å) is measured as the distance between the C1-C2 centroid and the C3-C4 centroid for and between the N1 and the C3-C4 centroid for (see Figure 6(a) for numbering).