Dispersion analysis of Rayleigh waves is performed to assess the velocity of complex structures such as sedimentary basins. At short periods several modes of the Rayleigh waves are often exited. To perform a reliable inversion of the velocity structure an identification of these modes is thus required. We propose a novel method to identify the modes of surface waves. We use the spectral ratio of the ground velocity for the horizontal components over the vertical component (H/V) measured on seismic coda. We then compare the observed values with the theoretical H/V ratio for velocity models deduced from surface wave dispersion when assuming a particular mode. We first invert the Rayleigh wave measurements retrieved from ambient noise cross-correlation with the assumptions that (1) the fundamental mode and (2) the first overtone are excited. Then we use these different velocity models to predict theoretical spectral ratios of the ground velocity for the horizontal components over the vertical component (H/V). These H/V ratios are computed under the hypothesis of equipartition of a diffuse field in a layered medium. Finally we discriminate between fundamental and higher modes by comparing the theoretical H/V ratio with the H/V ratio measured on seismic coda. In an application, we reconstruct Rayleigh waves from cross-correlations of ambient seismic noise recorded at seven broad-band stations in the Valley of Mexico. For paths within the soft quaternary sediments basin, the maximum energy is observed at velocities higher than expected for the fundamental mode. We identify that the dominant mode is the first higher mode, which suggests the importance of higher modes as the main vectors of energy in such complex structures.