The influence of rotational and geometrical isomerism on the nonlinear optical (NLO) properties, specifically the first-order hyperpolarizability ss, of chromophores of current interest has been investigated with density functional theory (DFT). In the first of this two-part study, the rotational isomerism of a linear chromophore was explored. Calculation of the torsion potentials about two of the rotatable and conformation-changing single bonds in a chromophore demonstrated the near equality of the molecular energies at 0 degrees and 180 degrees rotational angles. To explore the consequences of this near conformational energy degeneracy to NLO behavior, the eight low energy rotational isomers of FTC [Robinson, B. H.; et al. Chem. Phys. 1999, 245, 35] were investigated. This study provides the first-reported DFT-based calculation of the statistical mechanical average of, over the conformational space of a molecule having substantial nonlinear optical behavior. The influence of the solvent reaction field on rotameric populations and on the ss tensor is reported. In the second part, two molecules having two donors and two acceptors bonded respectively in ortho and meta positions on a central benzene ring are shown to have substantially different ss tensors. These two so-called molecular Xs have different highest occupied molecular orbital to lowest unoccupied molecular orbital (HOMO-LUMO) distributions, and consistent with expectations, it is found that the larger ss zzz is associated with a large spatial asymmetry between the HOMOs and LUMOs. Large hyperpolarizability correlates with the HOMO concentrated on the donor groups and the LUMO on the acceptor groups.