Photoemission studies (12 hv eV) of room-temperature formation of the Si-Cr interface show reactive behavior with atomic intermixing and dramatic modifications of the metal-derived d density of states. Self-consistent augmented-spherical-wave calculations of the total and l-projected densities of states for the silicides Cr3Si, CrSi, and CrSi3 in simplified cubic lattice structures allow an identification of general trends in the electronic structure upon Si-Cr heteropolar bond formation. These experimental and theoretical results suggest an interface morphology where a Si-rich intermixed phase is present for a depth of 10 monolayers between the Si crystal and the unreacted Cr film. Evidence of Si segregation in the top layers of the Cr film is provided. © 1982 The American Physical Society.