Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy.

Singlet fission is the spin-allowed conversion of a spin-singlet exciton into a pair of spin-triplet excitons residing on neighbouring molecules. To rationalize this phenomenon, a multiexcitonic spin-zero triplet-pair state has been hypothesized as an intermediate in singlet fission. However, the nature of the intermediate states and the underlying mechanism of ultrafast fission have not been elucidated experimentally. Here, we study a series of pentacene derivatives using ultrafast two-dimensional electronic spectroscopy and unravel the origin of the states involved in fission. Our data reveal the crucial role of vibrational degrees of freedom coupled to electronic excitations that facilitate the mixing of multiexcitonic states with singlet excitons. The resulting manifold of vibronic states drives sub-100 fs fission with unity efficiency. Our results provide a framework for understanding singlet fission and show how the formation of vibronic manifolds with a high density of states facilitates fast and efficient electronic processes in molecular systems.This is the author accepted manuscript. The final version is available from NPG via http://dx.doi.org/10.1038/nchem.237

Nonlinear Optics

This chapter provides a brief introduction into the basic nonlinear-optical phenomena and discusses some of the most significant recent advances and breakthroughs in nonlinear optics, as well as novel applications of nonlinear-optical processes and devices. Nonlinear optics is the area of optics that studies the interaction of light with matter in the regime where the response of the material system to the applied electromagnetic field is nonlinear in the amplitude of this field. At low light intensities, typical of non-laser sources, the properties of materials remain independent of the intensity of illumination. The superposition principle holds true in this regime, and light waves can pass through materials or be reflected from boundaries and interfaces without interacting with each other. Laser sources, on the other hand, can provide sufficiently high light intensities to modify the optical properties of materials. Light waves can then interact with each other, exchanging momentum and energy, and the superposition principle is no longer valid. This interaction of light waves can result in the generation of optical fields at new frequencies, including optical harmonics of incident radiation or sum- or difference-frequency signals