Theoretical studies of vibrationally excited polyatomic molecules using canonical Van Vleck perturbation theory

The highly excited vibrational states of polyatomic molecules are investigated using canonical Van Vleck perturbation theory, implemented in a superoperator framework. This approach is used to transform a vibrational Hamiltonian to a new representation which has a form ideally suited to the study of the dynamics of interest. The key advantage is that the solution to the full problem is obtained in the new representation using significantly smaller basis sets than are needed to obtain the solutions in the original representation. The transformations are applied to the Hamiltonian operator itself, not the Hamiltonian matrix; this superoperator approach obviates the need for large basis sets. The tedious and complex algebra, that is required to perform these transformations, is readily implemented with FORTRAN codes. Combining these two features has enabled the investigations of vibrational dynamics in energy regimes and densities of states, unattainable by standard methods. These methods are applied to two model problems and to the study of the highly excited overtones of CHD3 with up to five quanta of excitation in the CH bond.