Probing Homogeneous Line Broadening in CdSe Nanocrystals Using Multidimensional Electronic Spectroscopy.

The finite spectral line width of an ensemble of CdSe nanocrystals arises from size and shape inhomogeneity and the single-nanocrystal spectrum itself. This line width directly limits the performance of nanocrystal-based devices, yet most optical measurements cannot resolve the underlying contributions. We use two-dimensional electronic spectroscopy (2D ES) to measure the line width of the band-edge exciton of CdSe nanocrystals as a function of radii and surface chemistry.

Signatures of Herzberg-Teller coupling in three-dimensional electronic spectroscopy.

The coupling between electronic and nuclear variables is a key consideration in molecular dynamics and spectroscopy. However, simulations that include detailed vibronic coupling terms are challenging to perform, and thus a variety of approximations can be used to model and interpret experimental results. Recent work shows that these simplified models can be inadequate.

Experimental Detection of Branching at a Conical Intersection in a Highly Fluorescent Molecule.

Conical intersections are molecular configurations at which adiabatic potential-energy surfaces touch. They are predicted to be ubiquitous, yet condensed-phase experiments have focused on the few systems with clear spectroscopic signatures of negligible fluorescence, high photoactivity, or femtosecond electronic kinetics. Although rare, these signatures have become diagnostic for conical intersections.

Resolving molecular vibronic structure using high-sensitivity two-dimensional electronic spectroscopy.

Coherent multidimensional optical spectroscopy is an emerging technique for resolving structure and ultrafast dynamics of molecules, proteins, semiconductors, and other materials. A current challenge is the quality of kinetics that are examined as a function of waiting time. Inspired by noise-suppression methods of transient absorption, here we incorporate shot-by-shot acquisitions and balanced detection into coherent multidimensional optical spectroscopy.

Towards quantification of vibronic coupling in photosynthetic antenna complexes.

Photosynthetic antenna complexes harvest sunlight and efficiently transport energy to the reaction center where charge separation powers biochemical energy storage. The discovery of existence of long lived quantum coherence during energy transfer has sparked the discussion on the role of quantum coherence on the energy transfer efficiency. Early works assigned observed coherences to electronic states, and theoretical studies showed that electronic coherences could affect energy transfer efficiency--by either enhancing or suppressing transfer.