Theoretical investigation on isomerization and decomposition reactions of pentanol radicals-part I: branched pentanol isomers

Abstract

Theoretical investigations on the kinetics of decomposition and isomerization reactions for five types of branched pentanol radicals were carried out in this work. The M06-2X/6-311++G(d,p) level of theory was used...

Theoretical investigation on isomerization and decomposition reactions of pentanol radicals–part II: linear pentanol isomers

“…This difference may be attributed to the reason that the hydroxyl group adjacent to the breaking bond can increase the rate constant, as concluded in part I. 22 As for similar rate constants of other linear pentanol radicals in Fig. 15, it can be speculated that only the adjacent hydroxyl group to breaking bond can increase the rate constant, and those hydroxyl groups not adjacent to the breaking bond cannot change the rate constant which is independent of the distance.…”

“…To investigate the difference between linear and branched pentanol radicals, energy barriers for the same type of β-scission reaction at similar positions are compared in Table 3, where the data for branched pentanol radicals come from part I 22 of this work. The 4W4 radical and 6W5 radical can both produce ethenol and Ċ 3 H 7 radicals through the C–C bond β-scission reaction, but the energy barrier for the 6W5 radical is 0.5 kcal mol −1 higher than that for the 4W4 radical.…”

“…To investigate the kinetic differences between the branched and the linear pentanol radicals, rate constant comparisons are conducted for β-scission reactions of 3-methyl-1-butanol (4W) 22 and 1-pentanol (6W) radicals, as well as for 3-methyl-2-butanol (3W) 22 and 2-pentanol (7W) radicals. These comparisons considering isomers with similar hydroxyl group positions but different methyl group positions are shown in Fig.…”

“…2–4 are compared with the ones in the literature, as shown in Table 4. The species which were calculated in Part I 22 of this project are not discussed here. The heat capacities of these species are shown in Table 5.…”

“…1 shows the molecular geometries of the linear pentanol radical isomers, namely (a) 1-pentanol, (b) 2-pentanol, and (c) 3-pentanol, represented by 6W, 7W, and 8W, respectively. Rate constants and branching ratios for branched isomers of 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, and neo-pentanol radicals were discussed in part I 22 of this project, and we will focus on the kinetics of linear pentanol radicals in this work.…”