UC San Diego

We discuss theoretical approaches to nonlinear optical spectroscopy of molecular junctions. Optical response functions are derived in a form convenient for the implementation of Green function techniques, and their expressions in terms of pseudoparticle nonequilibrium Green functions are proposed. The formulation allows to account for both intramolecular interactions and hybridization of molecular states with those of contacts. Within a generic model and utilizing two-dimensional optical spectroscopy as an example, the methodology is compared with exact simulations and is shown to work where the traditional Liouville space approach fails.