Directional states of symmetric-top molecules produced by combined static and radiative electric fields

We show that combined electrostatic and radiative fields can greatly amplify the directional properties, such as axis orientation and alignment, of symmetric top molecules. In our computational study, we consider all four symmetry combinations of the prolate and oblate inertia and polarizability tensors, as well as the collinear and perpendicular (or tilted) geometries of the two fields. In, respectively, the collinear or perpendicular fields, the oblate or prolate polarizability interaction due to the radiative field forces the permanent dipole into alignment with the static field. Two mechanisms are found to be responsible for the amplification of the molecules' orientation, which ensues once the static field is turned on: (a) permanent-dipole coupling of the opposite-parity tunneling doublets created by the oblate polarizability interaction in collinear static and radiative fields and (b) hybridization of the opposite parity states via the polarizability interaction and their coupling by the permanent dipole interaction to the collinear or perpendicular static field. In perpendicular fields, the oblate polarizability interaction, along with the loss of cylindrical symmetry, is found to preclude the wrong-way orientation, causing all states to become high-field seeking with respect to the static field. The adiabatic labels of the states in the tilted fields depend on the adiabatic path taken through the parameter space comprised of the permanent and induced-dipole interaction parameters and the tilt angle between the two field vectors.