Abstract
Abstract A quartic force field for H 2 O 2 is presented in terms of curvilinear displacement coordinates, the result of an ab initio calculation with DZP, TZ2P, and TZ2P+ f basis sets. The MP2 method was used for the quadratic part with the SCF method used for the cubic and quartic parts. The MP2 calculations suggest that the equilibrium torsional angle is near 115°, rather than the currently accepted experimental value of 112°. Use of second-order perturbation theory leads to predictions for fundamentals which are within 1% of observed values. The quartic field was then changed so that the torsional part was represented in terms of cos nφ , to give a better description of the large amplitude motion. The vibrational energy levels of this new force field were then calculated by a six-dimensional variational vibrational analysis using an exact representation of the kinetic energy operator. Good agreement with experimental data was again achieved including low-lying torsional vibrations. Variationally calculated vibrational levels up to 6000 cm −1 are presented. The new potential is therefore shown, by the variational method, to be a good representation of the potential for H 2 O 2 in the region of the equilibrium geometry.
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