Spin-orbit mechanism of predissociation in the Wulf band of ozone

Previously calculated resonance widths of the ground vibrational levels in the electronic states 1 A ″ 3 ( A 2 3 ) and 1 A ′ 3 ( B 2 3 ) , which belong to the Wulf band system of ozone, are significantly smaller than observed experimentally. We demonstrate that predissociation is drastically enhanced by spin-orbit coupling between 1 A ″ 3 ∕ X A ′ 1 and 1 A ′ 3 ∕ 1 A ″ 3 . Multistate quantum mechanical calculations using ab initio spin-orbit coupling matrix elements give linewidths of optically bright components of the right order of magnitude.