Intraband Exciton Transitions in Photosynthetic Complexes Revealed by Novel Five-Wave-Mixing Spectroscopy.

We calculate the χ optical response of an oriented photosystem II reaction center of purple bacteria described by the Frenkel exciton model using nonlinear exciton equations (NEE). This approach treats each chromophore as an anharmonic oscillator and provides an intuitive quasiparticle picture of nonlinear spectroscopic signals of interacting excitons. It provides a computationally powerful description of nonlinear spectroscopic signals that avoids complete diagonalization of the total Hamiltonian.

Quantum Interferometric Pathway Selectivity in Difference-Frequency-Generation Spectroscopy.

Even-order spectroscopies such as sum-frequency generation (SFG) and difference-frequency generation (DFG) can serve as direct probes of molecular chirality. Such signals are usually given by the sum of several interaction pathways that carry different information about matter. Here we focus on DFG, involving impulsive optical-optical-IR interactions, where the last IR pulse probes vibrational transitions in the ground or excited electronic state manifolds, depending on the interaction pathway.

Quantum interferometry and pathway selectivity in the nonlinear response of photosynthetic excitons.

We propose a time-frequency resolved spectroscopic technique which employs nonlinear interferometers to study exciton-exciton scattering in molecular aggregates. A higher degree of control over the contributing Liouville pathways is obtained as compared to classical light. We show how the nonlinear response can be isolated from the orders-of-magnitude stronger linear background by either phase matching or polarization filtering.

Energy, Particle, and Photon Fluxes in Molecular Junctions.

Electroluminescence from a current-carrying molecular junction at steady state is simulated. (Charge) particle conservation and energy conservation are satisfied by a perturbative expansion in the radiation/matter coupling. Our approach makes it possible to adopt standard tools of traditional (equilibrium) spectroscopy to study signals from open systems such as molecular junctions.

Spontaneous Light Emission from Molecular Junctions: Theoretical Analysis of Upconversion Signal.

Spontaneous light emission from a current-carrying molecular junction is analyzed. There are two leading processes, fluorescence and electroluminescence, as defined using Liouville space diagrams within the perturbative method, that contribute to the light emission from junctions. This allows us to identify a general mechanism that explains the origin of the so-called upconversion electroluminescence (UCEL) signal, which has been observed in a variety of molecular junctions [Umera .