Pump-Probe Optical Response and Four-Wave Mixing in a Zinc-Phthalocyanine-Metal Nanoparticle Hybrid System.

We investigate theoretically the optical response of a zinc-phthalocyanine molecular quantum system near a gold spherical nanoparticle with a radius of 80 nm. The quantum system is irradiated by a strong pump and a weak probe coherent electromagnetic field. Using the density matrix methodology, we obtain analytical expressions for the absorption, dispersion, and the four-wave-mixing coefficients. The influence of the nanoparticle on the spontaneous decay rate of the quantum system, as well as on the external fields, are obtained by an electromagnetic Green's tensor method. The spectroscopic parameters of the molecule are also obtained by ab initio methods. For the studied optical spectra, we find that, below a critical distance between the molecule and the plasmonic nanoparticle, determined by the minimal value of the effective Rabi frequency, single-peaked spectra are observed. Above this critical distance, the spectra exhibit the characteristic Mollow-shaped profiles. The enhancement of the pump field detuning induces the shift of the sideband resonances away from the origin. Lastly, and most importantly, regardless of the value of the detuning, the optical response of the system is maximized for an intermediate value of the interparticle distance.