Formation of H3+ due to intramolecular bond rearrangement in doubly charged methanol

We report the formation of H-3(+) by proton coagulation in methanol under the impact of low energy Ar8+ projectiles. Our time-of-flight coincidence measurements with CH3OD establish that the H-3(+) formation arises from intramolecular bond rearrangement of the methyl group. We have performed ab initio quantum chemical calculations that show the preferred pathway for C-H-3 bond cleavage. Fragmentation of organic molecules like methanol under impact of highly charged ions is suggested as an alternative mechanism of H-3(+) formation in outer space.