On irradiating a molecular system with a laser beam of ultraviolet or visible frequency, photon absorption occurs when an electronic state is at a suitable energy level relative to an initial state. Despite meeting this criterion, interesting metastable states can remain inaccessible because of symmetry constraints. In this Letter a mechanism, based on the input of an off-resonant beam, is shown to enable the population of such states. This is achievable because the laser-modified process involves different selection rules compared to conventional photon absorption. The effects of applying the stimulus beam to either a one- or two-photon process are examined. (C) 2013 Elsevier B. V. All rights reserved.