Spectroscopic probe of the van der Waals interaction between polar molecules and a curved surface

We study the shift of rotational levels of a diatomic polar molecule due to its van der Waals interaction with a gently curved dielectric surface at temperature $T$, and submicron separations. The molecule is assumed to be in its electronic and vibrational ground state, and the rotational degrees are described by a rigid rotor model. We show that under these conditions retardation effects and surface dispersion can be neglected. The level shifts are found to be independent of $T$, and given by the quantum state averaged classical electrostatic interaction of the dipole with its image on the surface. We use a derivative expansion for the static Green's function to express the shifts in terms of surface curvature. We argue that the curvature induced line splitting is experimentally observable, and not obscured by natural linewidths and thermal broadening.

Figure 1

Parametrization of the profile of a gently curved dielectric surface near an atom or molecule.

Figure 2

Qualitative structure of the energy levels of a diatomic polar molecule in free space (left), near a planar surface (middle), and near a curved surface with different radii of curvature (right).