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At the intersection of spectroscopy and microscopy lie techniques that are capable of providing subnanometer imaging of excited states of individual molecules or nanoparticles. Such approaches are particularly important for imaging macromolecules or nanoparticles large enough to have a high probability of containing a defect. These inevitable defects often control properties and function despite an otherwise ideal structure. We discuss real-space imaging techniques such as using scanning tunneling microscopy tips to enhance optical measurements and electron energy-loss spectroscopy in a scanning transmission electron microscope, which is based on focused electron beams to obtain high-resolution spatial information on excited states. The outlook for these methods is bright, as they will provide critical information for the characterization and improvement of energy-switching, electron-switching, and energy-harvesting materials. [ABSTRACT FROM AUTHOR]

Multidimensional femtosecond time-resolved vibrational coherence spectroscopy allows one to investigate the evolution of vibrational coherence in electronic excited states. Methods such as pump-degenerate four-wave mixing and pump-impulsive vibrational spectroscopy combine an initial ultrashort laser pulse with a nonlinear probing sequence to reinduce vibrational coherence exclusively in the excited states. By carefully exploiting specific electronic resonances, one can detect vibrational coherence from 0 cm−1 to over 2,000 cm−1 and map its evolution. This review focuses on the observation and mapping of high-frequency vibrational coherence for all- trans biological polyenes such as β-carotene, lycopene, retinal, and retinal Schiff base. We discuss the role of molecular symmetry in vibrational coherence activity in the S1 electronic state and the interplay of coupling between electronic states and vibrational coherence. [ABSTRACT FROM AUTHOR]