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 with the M06-2X density functional and the 6-31+G(d,p) basis set using the 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, NICS(-1), NICS(0), and NICS(+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. Frontier molecular orbitals (FMOs) were generated using time-dependent density functional theory (TD-DFT) and the ωB97X-D/aug-cc-pvtz model chemistry with geometries optimized at the M06-2X/6-31+G(d,p) level of theory. All calculations were performed in the gas-phase.