We observe anharmonic decay of the photoexcited coherent A1g phonon in bismuth to points in the Brillouin zone where conservation of momentum and energy are satisfied for three-phonon scattering. The decay of a coherent phonon can be understood as a parametric resonance process whereby the atomic displacement periodically modulates the frequency of a broad continuum of modes. This results in energy transfer through resonant squeezing of the target modes. Using ultrafast diffuse x-ray scattering, we observe build up of coherent oscillations in the target modes driven by this parametric resonance over a wide range of the Brillouin zone. We compare the extracted anharmonic coupling constant to first principles calculations for a representative decay channel.Lattice anharmonicity governs a broad range of phenomena in condensed matter physics, from structural phase transitions [1] to heat transport and thermoelectricity [2,3]. Recent advances in first-principles calculations have allowed for precise calculations of thermal properties including effects due to phonon-phonon scattering [4][5][6]. However, experimental validation is indirect, mostly limited to bulk properties like the thermal conductivity, and experimental probes of the microscopic details of anharmonicity remain elusive. While scattering techniques like inelastic neutron scattering [7][8][9] and inelastic x-ray scattering [10][11][12][13] can measure quasiharmonic properties of phonons such as frequencies and linewidths across the Brillouin zone, these techniques lack the ability to resolve the individual decay channels of a given mode. Such a measurement would provide a unique view of the processes occurring during thermal equilibration, including a quantitative measurement of anharmonic force constants.Here, we report direct measurements of the anharmonic coupling of the zone center Raman active A 1g optic phonon in bismuth to longitudinal acoustic phonons at high wavevector, and extract an anharmonic coupling constant for a subset of these modes that is within an order of magnitude of that obtained by first-principles calculations. These measurements utilize femtosecond xray diffuse scattering to probe the temporal evolution of the phonon mean square displacements following optical excitation [14]. It was proposed in [15] that a parametric resonance of the zone-center mode with the acous-tic branch would be observable in femtosecond scattering measurements using an x-ray free electron laser (FEL).Bismuth is a group V semimetal that exhibits particularly strong electron-phonon coupling due to its Peierls distored structure, making it an ideal testbed for the study of large-amplitude phonon motion. Upon photoexcitation, the sudden change in the lattice potential causes the atoms to move coherently along the A 1g mode coordinate, resulting in a macroscopic modulation of both the optical reflectivity [16] and the Bragg peaks that are sensitive to the A 1g structure factor modulation [17][18][19].We use the theoretical framework developed in reference [15]...