Highly excited vibrational states of an isolated molecule encode the
vibrational energy flow pathways in the molecule. Recent studies have had
spectacular success in understanding the nature of the excited states mainly
due to the extensive studies of the classical phase space structures and their
bifurcations. Such detailed classical-quantum correspondence studies are
presently limited to two or quasi two dimensional systems. One of the main
reasons for such a constraint has to do with the problem of visualization of
relevant objects like surface of sections and Wigner or Husimi distributions
associated with an eigenstate. This neccesiates various alternative techniques
which are more algebraic than geometric in nature. In this work we introduce
one such method based on parametric variation of the eigenvalues of a
Hamiltonian. It is shown that the level velocities are correlated with the
phase space nature of the corresponding eigenstates. A semiclassical expression
for the level velocities of a single resonance Hamiltonian is derived which
provides theoretical support for the correlation. We use the level velocities
to dynamically assign the highly excited states of a model spectroscopic
Hamiltonian in the mixed phase space regime. The effect of bifurcations on the
level velocities is briefly discussed using a recently proposed spectroscopic
Hamiltonian for the HCP molecule.Comment: 12 pages, 9 figures, submitted to J. Chem. Phy