The ground-state geometries of DMAC-TRZ and DMAC-py-TRZ were optimized in the gas phase using density functional theory (DFT) at the M062X/6-31G(d) level of theory. The excited-state energies were calculated using time-dependent density functional theory (TD-DFT) within the Tamm-Dancoff approximation at the same level of theory (TDA-DFT). We employ the term "orthogonal" to describe the structure with a dihedral angle between the DMAC and the bridge that is close to 90 o and we dub as "bent" the structure with the small dihedral angle and V-shaped geometry of the DMAC.