Nonlinear Optical Rectification in an Inversion-Symmetry-Broken Molecule near a Metallic Nanoparticle.

Abstract

We study the nonlinear optical rectification of an inversion-symmetry-broken quantum system interacting with an optical field near a metallic nanoparticle, exemplified in a polar zinc–phthalocyanine molecule in proximity to a gold nanosphere. The corresponding nonlinear optical rectification coefficient under external strong field excitation is derived using the steady-state solution of the density matrix equations. We use ab initio electronic structure calculations for determining the necessary spectroscopic data of the molecule under study, as well as classical electromagnetic calculations for obtaining the influence of the metallic nanoparticle to the molecular spontaneous decay rates and to the external electric field applied to the molecule. The influence of the metallic nanoparticle to the optical rectification coefficient of the molecule is investigated by varying several parameters of the system, such as the intensity and polarization of the incident field, as well as the distance of the molecule from the nanoparticle, which indirectly affects the molecular pure dephasing rate. We find that the nonlinear optical rectification coefficient can be greatly enhanced for particular incident-field configurations and at optimal distances between the molecule and the metallic nanoparticle.