The photodissociation of ozone in the Hartley band: A theoretical analysis

Three-dimensional diabatic potential energy surfaces for the lowest four electronic states of ozone with A ′ 1 symmetry-termed X , A , B , and R -are constructed from electronic structure calculations. The diabatization is performed by reassigning corresponding energy points. Although approximate, these diabatic potential energy surfaces allow one to study the uv photodissociation of ozone on a level of theory not possible before. In the present work photoexcitation in the Hartley band and subsequent dissociation into the singlet channel, O 3 ( X ̃ ) + h ν → O ( D 1 ) + O 2 ( a Δ g 1 ) , are investigated by means of quantum mechanical and classical trajectory calculations using the diabatic potential energy surface of the B state. The calculated low-resolution absorption spectrum as well as the vibrational and rotational state distributions of O 2 ( a Δ g 1 ) are in good agreement with available experimental results.