Quantum monodromy and molecular spectroscopy

Abstract

Monodromy (or once round) is a classical property of integrable dynamical systems in two or more degrees of freedom, which imposes a characteristic pattern on the quantum mechanical eigenvalue distribution. This article explains the connection by showing how the presence of an isolated critical point of the Hamiltonian leads to a classical action function that is multi-valued with respect to energy and angular momentum. Consequently, by the Bohr correspondence principle between actions and quantum numbers, there can be no uniquely defined global system of quantum numbers. Implications for the interpretation of highly excited molecular spectra are brought out by reference to quasi-linear molecules, which transfer one degree of freedom from rotational to vibrational motion during the excitation process. Emphasis is placed on the simplest examples, while a brief resumé of the wide scope of the quantum monodromy phenomenon is given in the final section.