N2O was reacted with Li-n species both in the gas-phase under single-collision conditions and on the surface of large Ar-n (n approximate to 4000) clusters. In the gas-phase, a broad emission (410-730 nm) was attributed to LiOLi((A) over tilde B-1(1)) product from the reaction of Li-2. The same reaction on clusters leads a similar emission, but weaker to the blue. It is due to LiOLi((A) over tilde B-1(1)) also, but cooled before ejection off the cluster. Strong Li(2p P-2) emission is also observed in the cluster experiment presumably due to the reaction Li-3 + N2O LiOLi((X) over tilde (1)Sigma(g)(+)) + Li(2p P-2) + N-2 where Li(2p P-2) is ejected into the gas-phase. (C) 2002 Published by Elsevier Science B.V.