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The electroluminescence of molecules confined inside a nanocavity in thescanning tunneling microscopy possesses many intriguing but unexplainedfeatures. We present here a general theoretical approach based on the densitymatrix formalism to describe the electroluminescence from molecules near ametal surface induced by both electron tunneling and local surface plasmonexcitations simultaneously. It reveals the underlying physical mechanism forthe external bias dependent electroluminescence. The important role played bythe local surface plasmon on the electroluminescence is highlighted.Calculations for porphyrin derivatives have reproduced correspondingexperimental spectra and nicely explained the observed unusual large variationof emission spectral profiles. This general theoretical approach can find manyapplications in the design of molecular electronic and photonic devices.

A density matrix approach for the electroluminescence of molecules in a scanning tunneling microscope