The Degree of Ergodicity of ortho- and para-Aminobenzonitrile in an Electric Field

Abstract

We study the dynamics of the two molecules ortho-aminobenzonitrile (OABN) and para-aminobenzonitrile (PABN). They are structural isomers, with differing asymmetries and dipole moments. In this paper, we show that the dynamics of the system strongly depends on the region of phase space of the initial rotational state, the asymmetry of the molecule, and on the direction of the dipole. We also show that the ergodicity of the system varies gradually with energy, except where the rotational energy of the initial state is much less than the Stark interaction. In this regime, the projection of the dipole along the lab-frame z-axis varies linearly with increasing energy and follows the microcanonical ergodic estimate. Both molecules are far from full chaos for total angular momentum quanta J ∈ [0,45]. However, the initial rotational states in OABN access much more of the available phase space than in PABN. We show that this is a likely cause for the experimental discrepancies in molecular beam deflection experiments.

Ergodicity breaking in rapidly rotating C 60 fullerenes

“…This peculiar dynamical behavior arises from multiple avoided crossings with other vibrational states, which induce nonmonotonic variations in the molecule’s anisotropic character as J is varied. The rotational ergodicity transitions bear some similarity to those studied in asymmetric top molecules in a static electric field ( 35 , 36 ) in that both concern the transport of angular momentum in the molecule frame. However, unlike in ( 35 , 36 ), the rotational ergodicity transitions in 12 C 60 are induced by intramolecular rovibrational coupling in the freely rotating molecule, rather than by an externally applied electric field.…”