On the gas-phase reaction between SO₂ and O₂-(H₂O)_0-3 clusters - an ab initio study

TY - JOUR

T1 - On the gas-phase reaction between SO2 and O2-(H2O)0-3 clusters - an ab initio study

AU - Tsona, Narcisse T.

AU - Bork, Nicolai Christian

AU - Vehkamaki, Hanna

PY - 2014/4/7

Y1 - 2014/4/7

N2 - We present an ab initio investigation of the gas-phase reaction between SO2 and a O2-(H2O)n molecular cluster, n = 0-3. The associative product cluster, O 2SO2-(H2O)n, is formed with high energy gain although the binding energies decrease with increasing hydration. About 54 kcal mol-1 may be gained by isomerization of O2SO2-(H2O)n to the sulfate radical, SO4-(H2O)n, but a high energy barrier separates the two states. Although the isomerization is catalysed by the presence of a second SO2 molecule, the formation of SO4-(H2O)nvia O2 -(H2O)n and SO2 is found to be negligible under atmospheric conditions. At thermal equilibration at 298.15 K and 50% relative humidity the end products are mainly O2SO 2- and O2SO2-(H 2O)1. This journal is

AB - We present an ab initio investigation of the gas-phase reaction between SO2 and a O2-(H2O)n molecular cluster, n = 0-3. The associative product cluster, O 2SO2-(H2O)n, is formed with high energy gain although the binding energies decrease with increasing hydration. About 54 kcal mol-1 may be gained by isomerization of O2SO2-(H2O)n to the sulfate radical, SO4-(H2O)n, but a high energy barrier separates the two states. Although the isomerization is catalysed by the presence of a second SO2 molecule, the formation of SO4-(H2O)nvia O2 -(H2O)n and SO2 is found to be negligible under atmospheric conditions. At thermal equilibration at 298.15 K and 50% relative humidity the end products are mainly O2SO 2- and O2SO2-(H 2O)1. This journal is

U2 - 10.1039/c3cp54715a

DO - 10.1039/c3cp54715a

M3 - Journal article

C2 - 24549091

SN - 1463-9076

VL - 16

SP - 5987

EP - 5992

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 13

ER -