VIBRATIONAL-ROTATIONAL ANALYSIS OF THE HYDROGEN PEROXIDE CATION FROM AB INITIO POTENTIAL ENERGY AND DIPOLE MOMENT SURFACES

Author Institution: Citroil Aromatic, Inc., 320 Veterans Boulevard; Stevens Institute of Technology, 320 Veterans BoulevardResults of ab initio unrestricted Hartree-Fock self-consistent field and Meller-Plesset perturbation theory calculations for the hydrogen peroxide cation are reported. A $6-31G^{\ast\ast}$ basis set was employed to compute energies on an extensive grid of nuclear configurations near the planar equilibrium geometry $(R_{\infty}=1.32 A,, R_{OH}=1.00{\AA}, \angle_{H\infty}=104^{\circ})$. Analytical representations of potential energy and dipole moment surfaces were derived from least squares fits to the grid points and used to calculate spectroscopic constants, dipole moment expectation values and transition moments. A power series expansion to fourth degree in both normal and internal coordinates was used to obtain the spectroscopic constants, expectation values and intensities