Photon Antibunching in Single-Molecule Vibrational Sum-Frequency Generation

Abstract

Sum-frequency generation (SFG) allows for coherent upconversion of an electromagnetic signal and has applications in mid-infrared vibrational spectroscopy of molecules. Recent experimental and theoretical studies have shown that plasmonic nanocavities, with their deep sub-wavelength mode volumes, may allow to obtain vibrational SFG signals from a single molecule. In this article, we compute the degree of second order coherence ($g^{(2)}(0)$) of the upconverted mid-infrared field under realistic parameters and accounting for the anharmonic potential that characterizes vibrational modes of individual molecules. On the one hand, we delineate the regime in which the device should operate in order to preserve the second-order coherence of the mid-infrared source, as required in quantum applications. On the other hand, we show that an anharmonic molecular potential can lead to antibunching of the upconverted photons under coherent, Poisson-distributed mid-infrared and visible drives. Our results therefore open a path toward a new kind of bright and tunable source of indistinguishable single photons by leveraging ``vibrational blockade'' in a resonantly and parametrically driven molecule, without the need for strong light-matter coupling.