Quantum Mechanical calculation outputs for "Interplay Between Aromaticity and Triplet Photochemistry: π-Tropology and Positional Effects on the Triplet Behaviors of Pro-Aromatic Thioamides"

We optimized 4-Br-HHP, QDM 1, p-QDM 1, and p-QDM 2 in the S0 and T1 states using the M06-2X​ density functional and the 6-31+G(d,p)​​ basis set, as implemented in Gaussian 16 software.​ Vibrational analysis was used to ensure optimized structures are a minimum on their potential energy surface (i.e., all positive normal modes). To reduce computational costs and tame the conformational landscape, the long alkyl R groups in QDM 1, p-QDM 1, and p-QDM 2 were replaced with methyl groups. Nucleus-Independent Chemical Shift,​ NICSZZ(-1), NICSZZ(0), and NICSZZ(+1) calculations were performed at the M06-2X/6-31+G(d,p) level of theory by placing the probe in the geometric center of each ring and displacing it along the z-axis (perpendicular to conjugation plane) by -1Å, 0Å, or +1Å, respectively. Anistropy of Induced Current Density (AICD) plots were calculated at the M06-2X/6-31+G(d,p) level of theory using only contributions from π orbitals identified by visualizing the molecular orbitals at the same level of theory. Harmonic Oscillator Model of Aromaticity (HOMA) values were calculated for each ring in 4-Br-HHP, QDM 1, p-QDM 1, and p-QDM 2 in the S0 or T1 state. Frontier molecular orbitals (FMOs), Singly Occupied Molecular Orbitals (SOMOs), and vertical excitation energies were calculated using time-dependent density functional theory (TD-DFT) and the ωB97X-D​/aug-cc-pvtz​ model chemistry with the Integral Equation Formalism Polarizable Continuum Model (IEFPCM) for dichloromethane implicit solvation. All other calculations were performed in the gas-phase