Resonant interactions between discrete phonons in quinhydrone driven by nonlinear electron-phonon coupling

This study reports experimental, computational, and theoretical evidence for a previously unobserved coherent phonon-phonon interaction in an organic solid that can be described by the application of Fano's analysis to a case without the presence of a continuum. Using Raman spectroscopy of the hydrogen-bonded charge-transfer material quinhydrone, two peaks appear near 700 cm(-1) we assign as phonons whose position and line-shape asymmetry depend on the sample temperature and light scattering excitation energy. Density functional theory calculations find two nearly degenerate phonons possessing frequencies near the values found in experiment that share similar atomic motion out of the aromatic plane of electron donor and acceptor molecules of quinhydrone. Further analytical modeling of the steady-state light scattering process using the Peierls-Hubbard Hamiltonian and time-dependent perturbation theory motivates assignment of the physical origin of the asymmetric features of each peak's line shape to an interaction between two discrete phonons via nonlinear electron-phonon coupling. In the context of analytical model results, characteristics of the experimental spectra upon 2.33 eV excitation of the Raman scattering process are used to qualify the temperature dependence of the magnitude of this coupling in the valence band of quinhydrone. These results broaden the range of phonon-phonon interactions in materials in general while also highlighting the rich physics and fundamental attributes specific to organic solids that may determine their applicability in next generation electronics and photonics technologies.