Loss of water and hydrogen atom from the n-propanol molecular cation: A theoretical study

Abstract The unimolecular dissociation of n -propanol molecular cation ( 1 ) has been investigated theoretically. Density functional theory (DFT) molecular orbital calculations have been performed at the UB3LYP/aug-cc-pVQZ//UB3LYP/6-31 + G(d) level to obtain pathways for water and hydrogen atom loss from 1 . On the basis of the DFT results, the rate-energy dependences have been calculated for water and hydrogen atom loss from various deuterated analogues of 1 by Rice–Ramsperger–Kassel–Marcus modeling. The large kinetic deuterium isotope effects on the metastable water and hydrogen atom loss reported previously are rationalized from the obtained rate-energy dependences.