Propagation of surface acoustic modes on the (001) and (111) surfaces of Si coated by a thin isotropic overlayer is studied theoretically and experimentally. It is shown that when a surface acoustic wave (SAW) coexists with a pseudosurface wave (PSAW) of the uncoated substrate, the second-order acoustic mode of the film/substrate system originates from a PSAW and the first-order one from a SAW. The polarization pattern of either mode varies from Rayleigh type (saggital plane polarization) to Love type (horizontal polarization) depending on the propagation direction and the product of the wave vector q and film thickness d. It is also shown that the isolated off-symmetry pure mode point within the PSAW branch disappears at some critical qd value. Experimentally, surface acoustic modes of Ti-coated Si wafers are measured with the impulsive stimulated thermal scattering (ISTS) technique based on laser generation and detection of acoustic waves at a specified wave vector. ISTS data are shown to be determined by the surface elastodynamic Green function G(13)(omega,g). The measurements, only sensitive to Rayleigh-type waves, detect either the first- or the second-order mode, or both, depending on the qd and the observation angle. (C) 1999 American Institute of Physics. [S0021-8979(99)00317-5].