The 1(3)Σu (-)←X(3)Σg (-) transition of linear HC5H (A) has been observed in a neon matrix and gas phase. The assignment is based on mass-selective experiments, extrapolation of previous results of the longer HC2n+1H homologues, and density functional and multi-state CASPT2 theoretical methods. Another band system starting at 303 nm in neon is assigned as the 1(1)A1←X˜(1)A1 transition of the cumulene carbene pentatetraenylidene H2C5 (B).
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