Global analytical potential energy surfaces for HO2(XA″2) based on high-level <i>ab initio</i> calculations

Abstract

Two global analytical potential energy surfaces for the HO2(X2A") system have been developed by fitting approximately 15,000 ab initio points at the icMRCI+Qaug-cc-pVQZ level of theory, using the reproducing kernel Hilbert space method. One analytical potential is designed to give a very accurate representation of the low energy range that determines the vibrational spectrum, while the other attempts to provide a fast and uniformly accurate potential function for reaction dynamics. The quality of the fitted potential functions is confirmed by good agreement of the (J=0) HO2 vibrational spectrum and (J=0) quantum reaction probability for the H+O2(ji=0,nui=0) reaction with those obtained using the spline fitted potential. Quasiclassical trajectory calculations carried out on the new potential energy surface provided the reaction probability with a zero impact parameter (b=0), which is in reasonably good agreement with the J=0 quantum results.