In addition to an increased accuracy in the determination of structural parameters sub-\nDoppler spectroscopy of large molecules is shown to render valuable information about intramolecular\nprocesses and relaxation mechanisms. As an example we have measured the\nDoppler-free rotationally resolved two-photon spectrum of two vibronic bands of CsHs,\n1461; and 14i1;. Compared with the 14i1: band (EcxE :,:=css 2492 cm-') a drastically reduced\nnumber of sharp lines is observed in the 14i1; band (Eence=ss 3 412 cm-I). The X = 0\nrotational lines are still seen, while K # 0 lines disappear. This can be understood in terms\nof Coriolis coupling between the 14'1' state and other vibrational states within S1 and a\nsubsequent om-radiative process. This coupling might be the explanation for the drastic\nonset of line broadening in C6H6 at an excess energy of 3000 cm-', " channel three." The\nline broadening is then due to a different process from that responsible for the population\nlifetime of s1.