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 (3)A" ((3)A(2)) and 1 (3)A' ((3)B(2)), 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 (3)A"/X (1)A' and 1 (3)A'/1 (3)A". Multistate quantum mechanical calculations using ab initio spin-orbit coupling matrix elements give linewidths of optically bright components of the right order of magnitude.