Bifurcations of dividing surfaces in chemical reactions.

We study the dynamical behavior of the unstable periodic orbit (NHIM) associated to the non-return transition state (TS) of the H(2) + H collinear exchange reaction and their effects on the reaction probability. By means of the normal form of the Hamiltonian in the vicinity of the phase space saddle point, we obtain explicit expressions of the dynamical structures that rule the reaction. Taking advantage of the straightforward identification of the TS in normal form coordinates, we calculate the reaction probability as a function of the system energy in a more efficient way than the standard Monte Carlo method.

Dissipative-Hamiltonian decomposition of smooth vector fields based on symmetries.

We propose a method to decompose a smooth vector field into conservative and dissipative components. The procedure is based on the identification of the kernel of a linear operator associated with a given Hamiltonian combined with the use of Lie transformations for vector fields. Moreover, under certain conditions the nonconservative part of the splitting can be dropped at a given order of the transformation, obtaining after truncation, a Hamilton vector field.