DFT of EWG-functionalized Dipyrrolonaphthyridinedione (DPND) Annihilators

Triplet State Energies: Molecular geometry was optimized using the quantum chemistry program ORCA. Geometry optimization was performed at the B3LYP/3-21G level for both the singlet ground state (S0) and first excited triplet state (T1). The T1 energy was estimated as the adiabatic energy difference between the total energies of the S0 and T1 optimized geometries. Triplet Spin-Density:Geometry optimization was performed at the B3LYP/6-31G(d) level for the lowest lying triplet state (T1). Mulliken spin densities were extracted via Mulliken population analysis performed on the optimized triplet state geometry. Expectation value over each molecule equals to 2, indicating a triplet state. Positive and negative triplet spin density values indicate an excess of spin-up and spin-down electron density on each atom, respectively. Core-to-Aryl Dihedral Angle:Molecular geometry was optimized using the quantum chemistry program ORCA. Geometry optimization was performed at the B3LYP/6-31G(d) level for the lowest lying triplet state (T1). The core-to-aryl dihedral angle was determined from optimized geometries.