Hindered asymmetric top wavefunctions for three-dimensional H+H2

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Abstract
The perturbation technique for generating hindered asymmetric top rotor states for atom–diatom reactions described previously is applied to the H+H2 exchange reaction. The external rotation of the H3 system is that of an unhindered, nonrigid asymmetric top. Internal rotation (bending) of the system is described by hindered rotor functions of the internal angle. The method consists first of diagonalization of the energy matrix in the hindered symmetric top representation. The bending potential is modeled from the Porter–Karplus surface for H3. A limited number of the eigenfunctions obtained are then used as a basis for forming a matrix representation of the Coriolis–asymmetry coupling operators. A selection rule is derived which aids in the choice of hindered symmetric top basis states. The asymmetric top hindered rotor functions obtained are linear combinations of the unperturbed functions. Symmetry features of the hindered rotor functions are discussed. Numerical results are presented in the form of eation of the Coriolis–asymmetry coupling operators. A selection rule is derived which aids in the choice of hindered symmetric top basis states. The asymmetric top hindered rotor functions obtained are linear combinations of the unperturbed functions. Symmetry features of the hindered rotor functions are discussed. Numerical results are presented in the form of energy correlation diagrams and wavefunction plots.