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We analyse qualitatively the bending vibrational polyads of the acetylene molecule (CH) in the approximation of the resonant oscillator with axial symmetry using an effective vibrational Hamiltonian which reproduces bending vibrational energy levels computed by Michel Herman and coworkers [M. Herman, A. Campargue, M.I.E. Idrissi, and J.V. Auwera, J. Phys. Chem. Ref. Data 32 (3), 921 (2003). doi: 10.1063/1.1531651]. We explain how the classical limit of this quantum system for the total vibrational angular momentum is equivalent to a reduced perturbed Keplerian system on the classical phase space , such as the hydrogen atom in external electric and magnetic fields in the Kustaanheimo-Stiefel formalism. In particular, bending vibrational -polyads of CH correspond to the n-shells of the perturbed hydrogen atom. Within this approach, using the techniques developed for the Keplerian systems and methods of the qualitative theory, we account concisely for all series of bifurcations of the classical nonlinear normal modes and their manifestations in the quantum energy level spectrum described by our predecessors [V. Tyng and M.E. Kellman, J. Phys. Chem. B 110 (38), 18859 (2006). doi: 10.1021/jp057357f]. In addition to local oscillator approximations near stable equilibrium points, notably the local modes discussed by Rose and Kellman [J. Chem. Phys. 105 (24), 10743 (1996). doi: 10.1063/1.472882] and Jacobson et al. [J. Chem. Phys. 109 (1), 121 (1998). doi: 10.1063/1.476529; J. Chem. Phys. 111, 600 (1999). doi: 10.1063/1.479341; J. Chem. Phys. 110, 845 (1999). doi: 10.1063/1.478052], we introduce two new global integrable approximations, and confirm them by constructing respective two regular complementary lattices of quantum states within one -polyad. From the stratification of the phase space, we uncover the geometrical meaning of the corresponding new good quantum numbers and define new kind of wavefunction localisation in the neighbourhood of two spheres in the four-dimensional space. Furthermore, we use our two approximate lattices to uncover quantum monodromy of the system through the evolution of an elementary quantum cell along a closed path in the images of the nearly integrable energy-momentum maps. [ABSTRACT FROM AUTHOR]

Simple analytical formulas for the number of energy levels in the vibrational polyads are given. These formulas account for the resonances between the vibrational modes, and for the symmetry of the problem, so that the number of states of a particular symmetry type can be computed. The formulas are used to estimate the differential and integral densities of states from the minimum initial information about the molecule. Examples of the vibrational structure of triatomic molecules A3, tetrahedral molecules AB4, and linear molecules AB2 are considered. The analytical formulas are compared to the ab initio results for H3+ [J. R. Henderson et al., J. Chem. Phys. 98, 7191 (1993)]. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The structure of bending overtones of the H3+ and D3+ molecular ions at the energies below the barrier to linearity is analyzed using energies and wave functions from full three-dimensional discrete variable representation calculations. The lowest-in-energy states of the vibrational polyads ν2=4,5,6 are shown to follow the localization pattern of local bending modes, three equivalent-by-symmetry principal periodic trajectories of the corresponding classical two-mode system near the equilibrium. [ABSTRACT FROM AUTHOR]

Quantum monodromy is a non-trivial qualitative characteristic of certain non-regular lattices formed by the joint eigenvalue spectrum of mutually commuting operators. The latter are typically the Hamiltonian (energy) and the momentum operator(s) which label the eigenstates of the system. We give a brief review of known quantum systems with monodromy, which include such fundamental systems as the hydrogen atom in external fields, Fermi resonant vibrations of the CO2 molecule, and non-rigid triatomic molecules. We emphasize the correspondence between the classical Hamiltonian monodromy and its quantum analogue and discuss possible generalizations of this characteristic in classical integrable Hamiltonian dynamical systems and their quantum counterparts. [ABSTRACT FROM AUTHOR]

We describe the qualitative features of the joint spectrum of the quantum 1:1:2 resonant swing spring. The monodromy of the classical analogue of this problem is studied in Dullin et al. [Physica D 190, 15–37 (2004)]. Using symmetry arguments and numerical calculations we compute its three-dimensional (3D) lattice of quantum states and show that it possesses a codimension 2 defect characterized by a nontrivial 3D-monodromy matrix. The form of the monodromy matrix is obtained from the lattice of quantum states and depends on the choice of an elementary cell of the lattice. We compute the quantum monodromy matrix, that is the inverse transpose of the classical monodromy matrix. Finally we show that the lattice of quantum states for the 1:1:2 quantum swing spring can be obtained—preserving the symmetries—from the regular 3D-cubic lattice by means of three “elementary monodromy cuts.” [ABSTRACT FROM AUTHOR]

Intra- and interpolyad structures are investigated in the vibrational energy pattern of acetylene, using the spectroscopic Hamiltonian presented in previous papers in this series [see El Idrissi et al., J. Chem. Phys. 110, 2074 (1999)]. The existence of two constants of the motion is shown to generate very regular patterns in the manifold of vibrational energy levels. Distinct regular and oscillatory contributions are evidenced in the number of vibrational levels in the main polyads, which are fully reproduced using the generating function presented in Sadovskií and Zhilinskií [J. Chem. Phys. 103, 10520 (1995)]. Further developments of this approach are outlined. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We demonstrate how relative equilibria of a vibrating molecule, which are families of principal periodic orbits otherwise known as nonlinear normal modes, can be used to describe the global polyad structure of vibrational energy levels. The classical action integral n(E) computed along these orbits at different energies E corresponds to the polyad quantum number n so that the energy En of different relative equilibria describes the splitting of n-polyads. Further information on the internal polyad structure can be driven from the stability analysis of relative equilibria. We use the ozone molecule as a concrete example where n-polyads or "hyperpolyads" should be distinguished from the well-known polyads of the 1:1 stretching mode resonance; the stretching polyads are structural elements of hyperpolyads. We give dynamical interpretation of the relation between relative equilibria and n-polyads based on the normal form reduction in the limit of small vibrations near the equilibrium.

We consider the wide class of systems modeled by an integrable approximation to the 3 degrees of freedom elastic pendulum with 1:1:2 resonance, or the swing-spring. This approximation has monodromy which prohibits the existence of global action-angle variables and complicates the dynamics. We study the quantum swing-spring formed by bending and symmetric stretching vibrations of the CO2 molecule. We uncover quantum monodromy of CO2 as a nontrivial codimension 2 defect of the three dimensional energy-momentum lattice of its quantum states.