A new pump and probe technique for investigating vibrationally excited states via high resolution Raman spectroscopy is proposed. Ln a first step, a vibrational state, typically not accessible by a dipole moment transition from the ground state (BZ. forbidden, Raman allowed transition), is populated in a doubly pulsed stimulated Raman process. This state is long lived as the radiative decay to the ground state is highly inefficient. After a delay of several nanoseconds, the high resolution spectrum corresponding to a transition from this excited level is recorded. The second process follows the quasi-cw stimulated Raman spectroscopy scheme reported previously. Experimental aspects are discussed and the spectrum of 2 nu(1)-nu(1) of (CH4)-C-12 is presented as an illustration of the technique. The analysis of this spectrum has been done in two ways: first, by fitting simultaneously the nu(1) and 2 nu(1) bands using an isolated band model; second, using a model based on the tetradecad-pentad system. The standard deviations of both fits are of the order of the experimental precision. The interpretation of the spectroscopic constants of the corresponding models is discussed. (C) 1997 American Institute of Physics.