A new model for vibrationally assisted desorption induced by electronic transitions (DIET) is presented and applied to the laser-induced desorption of benzene from benzene multilayers on Pt {1 1 1}. A transient surface temperature rise initiated by laser pulse durations spanning the 150 fs to 200 ps time scale initially leads to vibrational excitation of chemisorbed benzene on Pt {1 1 1}. The remainder of the laser pulse then induces an electronic transition to an anti-bonding benzene-metal state from the vibrationally excited ground state. This opens up the possibility of photochemistry induced by low energy photons. (C) 2003 Elsevier B.V. All rights reserved.