Ab initio MO study on the solvent effect for hydrogen shift from hydrogen peroxide (H2O2) to water oxide (O-OH2)

Ab initio molecular orbital calculation was performed to study hydrogen shi ft from hydrogen peroxide (H2O2, 1) to water oxide (O-OH2, 2) under the inv olvement of nH(2)O molecules (n = 0-3). Calculation suggests that there exi sts a concerted proton-relay mechanism ([1, k]-type hydrogen shift (k = 4,6 ,8) passing through a single transition structure, TS) having more reduced activation energy than that of direct hydrogen 1,2-shift. In proton-relay m echanism, hydrogen atom is successively delivered along hydrogen bonding H2 O molecules. (C) 2001 Elsevier Science B.V. All rights reserved.