Can Anti-Aufbau DFT Calculations Estimate Singlet Excited State Aromaticity? Correspondence on 'Dibenzoarsepins: Planarization of 8 pi-Electron System in the Lowest Singlet Excited State'

摘要

The simple anti-aufbau DFT approach for estimating singlet excited state aromaticity suggested in a recent Communication published in this journal is shown to produce incorrect results because it targets a linear combination of the singlet and triplet configurations involving the HOMO and LUMO rather than the first singlet excited state. If the S-1 state of a molecule is dominated by the HOMO -> LUMO excitation, a comparably simple but theoretically consistent and qualitatively correct approximation to the S-1 wavefunction can be achieved by performing a small "two electrons in two orbitals" CASSCF(2,2) calculation which can be followed by the evaluation of magnetic aromaticity criteria such as NICS.