Construction of Darboux coordinates and Poincaré–Birkhoff normal forms in noncanonical Hamiltonian systems

Abstract

We demonstrate a general method to construct Darboux coordinates via normal form expansions in noncanonical Hamiltonian system obtained from e.g. a variational approach to quantum systems. The procedure serves as a tool to naturally extract canonical coordinates out of the variational parameters and at the same time to transform the energy functional into its Poincaré–Birkhoff normal form. The method is general in the sense that it is applicable for arbitrary degrees of freedom, in arbitrary orders of the local expansion, and it is independent of the precise form of the Hamilton operator. The method presented allows for the general and systematic investigation of quantum systems in the vicinity of fixed points, which e.g. correspond to ground, excited or transition states. Moreover, it directly allows to calculate classical and quantum reaction rates by applying transition state theory.