The Huggins band of ozone: A theoretical analysis

The Huggins band of ozone is investigated by means of dynamics calculations using a new (diabatic) potential energy surface for the 3 (1)A(')(B-1(2)) state. The good overall agreement of the calculated spectrum of vibrational energies and intensities with the experimental spectrum, especially at low to intermediate excitation energies, is considered as evidence that the Huggins band is due to the two C-s potential wells of the B-1(2) state rather than the single C-2v well of the 2 (1)A(')((1)A(1)) state. The vibrational assignment of the cold bands, based on the nodal structure of wave functions, on the whole supports the most recent experimental assignment [J. Chem. Phys. 115, 9311 (2001)]. The quantum mechanical spectrum is analyzed in terms of classical periodic orbits and the structure of the classical phase space.(C) 2004 American Institute of Physics.