HOMER: a reparameterization of the harmonic oscillator model of aromaticity (HOMA) for excited states

Excited-state aromaticity (ESA) and antiaromaticity (ESAA) are by now well-established concepts for explaining photophysical properties and photochemical reactivities of cyclic, conjugated molecules. However, their application is less straightforward than the corresponding process by which the thermal chemistry of such systems is rationalized in terms of ground-state aromaticity (GSA) and antiaromaticity (GSAA). Recognizing that the harmonic oscillator model of aromaticity (HOMA) provides an easy way to measure aromaticity on geometric grounds, it is therefore notable that this model is yet to be parameterized for excited states. Against this background, we here present a new parameterization of HOMA - termed HOMER - for the T-1 state of both carbocyclic and heterocyclic compounds based on high-level quantum-chemical calculations. Considering CC, CN, NN and CO bonds and testing the parametrization using calculated magnetic data as reference, we find that the description of ESA and ESAA by HOMER is superior to that afforded by the original HOMA scheme, and that it reaches the same overall quality as HOMA does for GSA and GSAA. Furthermore, we demonstrate that the derived HOMER parameters can be used for predictive modeling of ESA and ESAA at very different levels of theory. Altogether, the results highlight the potential of HOMER to facilitate future studies of ESA and ESAA.

Automated summary

Excited-state aromaticity (ESA) and antiaromaticity (ESAA) are well-established concepts in explaining the photophysical properties and reactivities of cyclic, conjugated molecules. In this study, a new parameterization of the harmonic oscillator model of aromaticity (HOMA) called HOMER is presented for the T-1 state of carbocyclic and heterocyclic compounds. The results demonstrate that HOMER provides a superior description of ESA and ESAA compared to the original HOMA scheme, and can be used for predictive modeling of ESA and ESAA at different levels of theory.