In this paper the authors use the optimal internal vibrational coordinates previously determined for the electronic ground state of the ozone molecule to study the vibrational spectrum of the molecule employing the second empirical potential energy surface calculated by Tyuterev et al. [Chem. Phys. Lett. 316, 271 (2000)]. First, the authors compute variationally all the bound vibrational energy levels of the molecule up to the dissociation limit and state the usefulness of the optimal coordinates in this respect, which allows us to converge all the bound levels using relatively small anharmonic basis sets. By analyzing the expansion coefficients of the wave functions, they show then that a large portion of the vibrational spectrum of O3 can be structured in nearly separable polyadic groups characterized by the polyad quantum number N=n1+n2+n(theta) corresponding to the optimal internal coordinates. Accordingly, they determine an internal effective vibrational Hamiltonian for O3 by fitting the effective Hamiltonian parameters to the experimental vibrational frequencies, using as input parameters in the fit those extracted from an analytical second-order Van Vleck perturbation theory calculation. It is finally shown that the internal effective Hamiltonian thus obtained accurately describes the vibrational spectrum of ozone in the low and medium energy regimes.
The use of generalized internal coordinates for the variational calculation of excited vibrational states of symmetrical bent triatomic molecules is considered with applications to the SO2, O3, NO2, and H2O molecules. These coordinates depend on two external parameters which can be properly optimized. We propose a simple analytical method to determine the optimal internal coordinates for this kind of molecules based on the minimization with respect to the external parameters of the zero-point energy, assuming only quadratic terms in the Hamiltonian and no quadratic coupling between the optimal coordinates. The optimal values of the parameters thus obtained are shown to agree quite well with those that minimize the sum of a number of unconverged energies of the lowest vibrational states, computed variationally using a small basis function set. The unconverged variational calculation uses a basis set consisting of the eigenfunctions of the uncoupled anharmonic internal coordinate Hamiltonian. Variational calculations of the excited vibrational states for the four molecules considered carried out with an increasing number of basis functions, also evidence the excellent convergence properties of the optimal internal coordinates versus those provided by other normal and local coordinate systems.
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