Higher-order carbon sulfides - carbon tetrasulfide (CS4; D 2d), carbon pentasulfide (CS5; C2), and carbon hexasulfide (CS6, C2) - were detected for the first time via infrared spectroscopy in low temperature carbon disulfide (CS2) ices upon irradiation with energetic electrons. The identification of these molecules was aided via observed band positions of their C-12 and C-13 isotopologues and the agreement with vibrational modes and isotope shifts predicted from ab initio calculations. Reaction pathways to these species are discussed as well. © 2013 Elsevier B.V. All rights reserved.