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

Table 1

Characteristic geometry parameters of the fully optimized structures using B3LYP and MP2 compared to the lowest-lying CT electronic transition. See Scheme 2.

	B3LYP geometry				MP2 geometry
								f
oe-1	180	0.059	3.03	1.254	148.7	0.078	3.04	1.096
oe-2	180	0.058	2.71	1.587	146.9	0.075	2.73	1.370
oe-3	180	0.057	2.46	1.880	145.5	0.073	2.50	1.636
oy-1	180	0.098	2.97	1.048	148.4	0.112	2.96	0.892
oy-2	180	0.104	2.61	1.128	147.4	0.115	2.63	0.993
oy-3	180	0.105	2.34	1.077	147.0	0.116	2.31	0.944

The pyramidalization of the amine group is measured by the dihedral angle C1-N1-C2-C3 (in degrees). The bond length alternation (BLA, in Å) is computed as described in Section 2. The calculation of the BLA for oe-1 is exemplified in the graph. Theoretical () and experimental () energy of the lowest-lying CT electronic transition (in eV). Data extracted from [12]. Data from [23].