Table 1. Physical properties calculated using the ωB97X-D functional. The Frontier orbital energies, ε _H (HOMO) and ε _L (LUMO), are in good agreement with the ionization potential (IP) and the electron affinity (EA), respectively, indicating physically meaningful Kohn–Sham orbitals. The dipole moments (μ) vanish for Class I and Class III molecules and are sizable for Class II molecules. The quadrupole moments (Q) tend to increase with the number of fluorine atoms. The intermolecular separation (a) for Class I molecules was set to the distance between the molecular centers of mass (c.o.m.), and for Class II and III molecules it was set to the distance between the molecular planes. The intermolecular binding energies (F _inter), electronic coupling for hole transport (Γ _h), and hole transport reorganization energy (calculated using dimers, Eh,dr and monomers, Eh,mr) reveal significant differences between the three molecular classes.

Cl.	Molecule	ε H [eV]	ε L [eV]	IP [eV]	EA [eV]	μ [D]	Q xx [D Å]	Q yy [D Å]	Q zz [D Å]	a [Å]	F inter [eV]	Γ h [eV]	E h,d r [eV]	E h,m r [eV]
6-31G(d)
I	Naph	–7.73	0.84	7.75	–0.81	0.00	–62.5	–50.2	–49.6	5.00	–0.337	0.001	0.266	0.236
	Naph-F8	–8.38	–0.11	8.32	0.22	0.00	–99.8	–101.1	–89.3	5.99	–0.264	0.005	0.545	0.458
II	Naph-F4-C1	–8.00	0.33	7.98	–0.24	3.95	–75.1	–70.2	–75.9	3.35	–0.562	0.086	0.422	0.362
	Naph-F4-C2	–8.08	0.35	8.05	–0.27	2.90	–75.8	–75.8	–70.1	3.37	–0.588	0.110	0.454	0.380
III	Naph-F4-T1	–8.03	0.27	8.00	–0.20	0.00	–83.5	–67.1	–75.8	3.51	–0.563	0.380	0.424	0.394
	Naph-F4-T2	–8.35	0.27	8.58	–0.16	0.00	–89.7	–66.8	–75.9	3.50	–0.471	0.378	0.335	0.330
	Pele-F6-T	–7.24	–0.71	7.04	0.93	0.03	–151.6	–126.9	–140.7	3.54	–1.183	0.206	0.318	0.299
cc-pVTZ
	Naph-F4-T2	–8.57	0.03	8.72	–0.15	0.00	–92.0	–68.0	–76.7	3.50	–0.437	0.363	0.331	0.311