Photodissociation spectra of Co-n(+)(CH3OH)(3) (n = 1-3) were measured in the region of 2800-6800 cm(-1). A broad near-infrared (-IR) absorption was observed in the spectra of n = 2 and 3, in addition to the vibrational absorption in the mid-IR region. With the aid of a calculation based on time-dependent density functional theory (TD-DFT), the near-IR absorption is assigned to the electronic transitions between the levels located near the highest occupied and the lowest unoccupied levels of Co-n(+)(CH3OH)(3), in which one or two methanol molecules dissociate to CH3 and OH fragments and the fragments adsorb on the bridge sites of Co-n(+). (C) 2010 Elsevier B.V. All rights reserved.