Collective Molecular Superrotation: A Model for Extremely Flexible Molecules Applied to Protonated Methane.

The concept of molecular structure is traditionally considered to be virtually fundamental. However, it breaks down in extremely flexible molecules, whose dynamics are governed by large-amplitude motions. For the dynamics of molecules with free internal rotations, we therefore propose a five-dimensional rigid rotor model, with states characterized by two generalized angular momentum quantum numbers and a rotational constant B. The quantum numbers characterize a 5D angular-momentum vector, super-j, which describes collective rotations that involve both the internal and the overall rotation. This model predicts the lowest energy states of the prototypical, extremely flexible molecule, CH_{5}^{+}. Both energies and symmetries compare very favorably to recent experimental results. The respective assignment to the new quantum numbers indicates the validity of our concept of collective rotations in extremely flexible molecules.