Pentacene is one of the most investigated candidates for organic thin film transistor (OTFT) applications over the last few decades even though it unstable in air (E-g = 1.80 eV), owing in part to its planar nature and high charge-transfer mobilities as both a single crystal (35 cm(2) V-1 s(-1)) and as a thin-film (3.0 cm(2) V-1 s(-1)). Until now, picene is the only isomer of pentacene to be investigated for organic electronic applications, due to its greater stability (E-g = 4.21 eV) and high-charge transfer mobility (3.0 cm(2) V-1 s(-1)); even benefiting from oxygen doping. In the present study, a total of 12 fused-ring isomers (including pentacene, picene and ten other structures) of the formula C22H14 were analyzed and investigated for their electronic and optical properties for worth in OTFT applications. We screened several pure and hybrid DFT functionals against the experimental frontier molecular orbitals (FMOs) of pentacene, then deployed Marcus Theory, Koopmans' Theorem and Green's function with the P3 electron propagator variant, for the internal hole reorganization energy, the hole transfer integral (via the "splitting-in-dimer method" at d = 3.0, 3.5, and 4.0 angstrom), the charge transfer rate constant, and vertical ionization energies. Using these as a basis, we studied pentacene's isomers and found that the four nonplanar structures, namely, benzo[g]chrysene (3), naphtho[c]phenanthrene (7), benzo[c]chrysene (11) and dibenzo[c,c']phenthrene (12), are (I) more stable than pentacene, by up to 2 eV, and (II) have relatively similar ionization energies (7.5-7.6 eV) to those of picene's experimental value (7.51 eV). The largest charge transfer rates at 3.5 A dimer separations were given by the isomers benzo[b]chrysene 4, naphtha[c]phenanthrene 7, dibenzo[a,c]anthracene 8 and benzo[a]tetracene 10 and found to be 2.92, 1.72, 1.30, and 3.09 X 10(14) s(-1) respectively. In comparison to that of pentacene (K-CT = 3.97 x 10(14) s(-1)), these unusual isomers are thus promising air-stable and alternative candidates for organic electronic applications.