Passive laser irradiation as a tool for optical catalysis

The mechanisms of absorption, emission, and scattering of photons form the foundations of optical interactions between light and matter. In the vast majority of such interactions there is a significant interplay and energy exchange between the radiation field and the material components. In absorption for example, modes of the field are depopulated by photons whose energy is at resonance with a molecular transition producing excited material states. In all such optical phenomena, the initial state of the radiation field differs in mode occupation to its final state. However, certain optical processes can involve off-resonance laser beams that are unchanged on interaction with the material: the output light, after interaction, is identical to the laser input. Such off-resonance interactions include forward Rayleigh scattering, responsible for the wellknown gradient force in optical trapping, and the laser-induced intermolecular interaction commonly termed optical binding; in both processes, an intense beam delivers its effect without suffering change. It is possible for beams detuned from resonance to provide not only techniques for optomechanical and optical manipulation, but also to passively influence other important and functional interactions such as absorption from a resonant beam, or energy transfer. Such effects can be grouped under the banner of 'optical catalysis', since they can significantly influence resonant processes. Furthermore, off-resonance photonics affords a potential to impact on chemical interactions, as in the passive modification of rotational constants and phase transitions. To date, apart from optical manipulation, the potential applicability of passive photonics, particularly in the realm of chemical physics and materials science, has received little attention. Here we open up this field, highlighting the distinct and novel role that off-resonance laser beams and the ensuing photonics can play.