Pathways for intramolecular relaxation in S
1
benzene
Sub-Doppler spectra of various one- and two-photon vibronic bands of benzene are discussed and analysed to determine the pathways of intramolecular relaxation for Sx benzene. New results are presented for the 14J1q16| band of C 6 H 6 and the 14^1^ band of 13 C 6 H 6 . The decay behaviour depends strongly on the excess energy and the rotational quantum numbers rather than on the vibrational character and symmetry of the excited state. At low vibrational excess energy the pathway for intramolecular relaxation is a coupling in the strong limit between pairs of states in Sx leading to shifts of lines, whereas at intermediate excess energy coupling in the weak limit to background states in Sx is present. These background states are strongly broadened due to a fast electronic non-radiative process. The intramolecular relaxation is found to be initiated by the coupling to the broadened S 1 background states and energy can flow via these states to the T 1 or S 0 state. The rotationally selective disappearance of lines is believed to be due to an intricate interplay of the rotational dependence of the coupling matrix elements and accidental resonances, which lead to interference of possible decay channels.