Real-time mapping of electronic structure with single-shot two-dimensional electronic spectroscopy

Electronic structure and dynamics determine material properties and behavior. Important time scales for electronic dynamics range from attoseconds to milliseconds. Two-dimensional optical spectroscopy has proven an incisive tool to probe fast spatiotemporal electronic dynamics in complex multichromophoric systems. However, acquiring these spectra requires long point-by-point acquisitions that preclude observations on the millisecond and microsecond time scales. Here we demonstrate that imaging temporally encoded information within a homogeneous sample allows mapping of the evolution of the electronic Hamiltonian with femtosecond temporal resolution in a single-laser-shot, providing real-time maps of electronic coupling. This method, which we call GRadient-Assisted Photon Echo spectroscopy (GRAPE), eliminates phase errors deleterious to Fourier spectroscopies while reducing the acquisition time by orders of magnitude using only conventional optical components. In analogy to MRI in which magnetic field gradients are used to create spatial correlation maps, GRAPE spectroscopy takes advantage of a similar type of spatial encoding to construct electronic correlation maps. Unlike magnetic resonance, however, this spatial encoding of the nonlinear polarization along the excitation frequency axis of the two-dimensional spectrum results in no loss in signal while simultaneously reducing overall noise. Correlating the energy transfer events and electronic coupling occurring in tens of femtoseconds with slow dynamics on the subsecond time scale is fundamentally important in photobiology, solar energy research, nonlinear spectroscopy, and optoelectronic device characterization.