Gaussian boson sampling of ozone: Vibronic structure of the Wulf band and intersystem crossing rate

Abstract

Gaussian Boson Sampling (GBS) was applied to describe photophysics of ozone. One million Franck–Condon configurations were generated to model the Wulf-band vibronic progression and to compute the intersystem crossing rate constant. The calculated value of $k_{\mathrm{ISC}}$ ranges from 10⁹ to 10¹⁰ s⁻¹ depending on the approach used. Although ozone has an unusually large vibrational frequency ratio between the initial and final electronic states and non-negligible Duschinsky rotation, neglecting both effects in the linear-coupled approximation yields nearly identical results. The study demonstrates that GBS can yield accurate vibronic spectra and ISC rate constants at a computational cost inaccessible to classical summations.