The binding energy of the NO-CH4 van der Waals complex has been determined by velocity map imaging to be 198 +/- 2 cm(-1) in the X state, with a corresponding (chi) over tilde state value of 103 +/- 12 cm(-1). Individual rotational states of the NO A products have been probed, providing insight into the correlated motion of the NO and CH4 products. Low rotation of NO correlates with low rotation of CH4. With increasing rotational excitation in NO there is a corresponding increase in CH4 rotational excitation. At the highest NO rotation, the CH4 is forced through conservation of energy to be in low rotational states. (c) 2006 Elsevier B.V. All rights reserved.