Circularly polarized light-induced potentials and the demise of excited states.

Abstract

In the presence of strong electric fields, the excited states of single-electron molecules and molecules with large transient dipoles become unstable because of anti-alignment, the rotation of the molecular axis perpendicular to the field vector, where bond hardening is not possible. We show how to overcome this problem by using circularly polarized electromagnetic fields. Using a full quantum description of the electronic, vibrational, and rotational degrees of freedom, we characterize the excited electronic state dressed by the field and analyze its dependence on the bond length and angle and the stability of its vibro-rotational eigenstates. Although the dynamics is metastable, most of the population remains trapped in this excited state for hundreds of femtoseconds, allowing quantum control. Contrary to what happens with linearly polarized fields, the photodissociation occurs along the initial molecular axis, not perpendicular to it.