Understanding the origin of electron-phonon coupling in lead halide perovskites is key to interpreting and leveraging their optical and electronic properties. Here we show that photoexcitation drives a reduction of the lead-halide-lead bond angles, a result of deformation potential coupling to low-energy optical phonons. We accomplish this by performing femtosecond-resolved, optical-pump-electron-diffraction-probe measurements to quantify the lattice reorganization occurring as a result of photoexcitation in nanocrystals of FAPbBr(3). Our results indicate a stronger coupling in FAPbBr(3) than CsPbBr(3). We attribute the enhanced coupling in FAPbBr(3) to its disordered crystal structure, which persists down to cryogenic temperatures. We find the reorganizations induced by each exciton in a multi-excitonic state constructively interfere, giving rise to a coupling strength that scales quadratically with the exciton number. This superlinear scaling induces phonon-mediated attractive interactions between excitations in lead halide perovskites.

Conjugated molecules with phenylethynyl building blocks are usually characterised by torsional disorder at room temperature. They are much more rigid in the electronic excited state due to conjugation. As a consequence, the electronic absorption and emission spectra do not present a mirror-image relationship. Here, we investigate how torsional disorder affects the excited state dynamics of 9,10-bis(phenylethynyl)anthracene in solvents of different viscosities and in polymers, using both stationary and ultrafast electronic spectroscopies. Temperature-dependent measurements reveal inhomogeneous broadening of the absorption spectrum at room temperature. This is confirmed by ultrafast spectroscopic measurements at different excitation wavelengths. Red-edge irradiation excites planar molecules that return to the ground state without significant structural dynamics. In this case, however, re-equilibration of the torsional disorder in the ground state can be observed. Higher-energy irradiation excites torsionally disordered molecules, which then planarise, leading to important spectral dynamics. The latter is found to occur partially via viscosity-independent inertial motion, whereas it is purely diffusive in the ground state. This dissimilarity is explained in terms of the steepness of the potential along the torsional coordinate.