Dipole-Dipole Interaction in Two-Photon Spectroscopy of Metallic Nanohybrids

We have developed a theory for the two-photon fluorescence in nanohybrids made of an ensemble of metallic nanorod shells and an ensemble of quantum emitters. A metallic nanorod shell is made of a metallic rod and dielectric shell. We consider that the quantum emitters are four-level quantum systems. When a probe laser light falls on the metallic nanorod shells, the surface plasmon polariton electric field is produced at the interface between the metallic nanorod and dielectric shell. This electric field, along with the probe field, induces dipoles in the quantum emitters and nanorod shells. These dipoles interact with each other via the dipole-dipole interaction. The two-photon fluorescence has been calculated by using the quantum density matrix method in the presence of the dipole-dipole interaction (coupling). Analytical expressions of the two-photon fluorescence have been derived in the presence of the dipole-dipole interaction. We showed that that the two-photon process is made of two terms. The first term is the two-photon process due to the two probe field photons. On other the hand, the second term is made of one DDI field photon and one probe field photon. It is found that the surface plasmon polariton resonance energy is not resonant with the exciton energy, the two-photon fluorescence spectrum splits from one peak to three peaks. The splitting in the spectrum is due to the presence of the dressed states created in the system due to the strong dipole-dipole interaction. We also compared our theory with the experimental data of the metallic nanohybrid system made of metallic nanorod shells and quantum emitters (T790 molecules) and found a good agreement between the theory and the experiments.