Unconventional control of excited states of a dimer molecule by a localized light field between metal nanostructures

We have made a theoretical study of the spatial interplay between the localized light field (LLF) and the electronic wavefunction of molecules. When the LLF has a nanoscale spatial variation comparable to a molecular wavefunction, this interplay is crucial to determine the optical response of molecular excited states. Such a condition can be realized in case that a molecule is lying in the vicinity of a metal nanogap. By using the calculation method applicable to arbitrary‐shaped samples, we demonstrate a drastic enhancement of the response electromagnetic field from an optical forbidden state whose magnitude is comparable to that from an allowed state. The obtained result indicates that we have a possibility to control the excited states of molecules by designing the LLF with metal nanostructures. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)