Spectroscopy in sculpted fields

SummaryMetallic and magnetic nanostructures set electromagnetic boundary conditions which can lead to highly contorted fields in their immediate vicinity. While much attention has been devoted to enhancements in electric field strength, we argue that equally interesting phenomena arise from enhancements in magnetic and electric field gradients. Nonuniform fields near nanostructures can induce molecular transitions that are forbidden by electric dipole selection rules. We illustrate this claim with two examples. “Superhelical” electromagnetic fields are predicted to show enhanced asymmetry in their interaction with chiral molecules, far greater than that due to circularly polarized light. Such fields could be used to induce chiral photochemistry with large enantiomeric excess. Steeply varying DC magnetic fields are predicted to enhance the rate of intersystem crossing in molecular bi-radicals. Such fields could provide a route to new nanomagnetic catalysts and to magnetic control of chemical reactions.