TY - JOUR
T1 - A model study on the mechanism and kinetics for reactions of the hydrated electron with H3O+ and NH4 + ions
AU - Huyen, Trinh Le
AU - Pham, Tien V.
AU - Nguyen, Minh Tho
AU - Lin, Ming-Chang
N1 - Publisher Copyright:
© 2019 Elsevier B.V.
PY - 2019/9/16
Y1 - 2019/9/16
N2 - Mechanism and kinetics of the reactions of the hydrated electron (e−aq) with H3O+ and NH4+ cations were determined using quantum chemical computations with both density functional theory (B3LYP) and wavefunction (MP2 and CCSD(T)) methods and the 6-311++G(3df,2p) basis set, in conjunction with a PCM method for treating structures in solution. Although both reactions occur with a hydrogen atom transfer, their mechanisms differ from each other by kinetic results. While the reaction of e−aq and H3O+ in solution is diffusion-controlled, NH4+ reacts with e−aq via a transition structure with H-tunneling. The predicted rate constants agree well with available experimental results.
AB - Mechanism and kinetics of the reactions of the hydrated electron (e−aq) with H3O+ and NH4+ cations were determined using quantum chemical computations with both density functional theory (B3LYP) and wavefunction (MP2 and CCSD(T)) methods and the 6-311++G(3df,2p) basis set, in conjunction with a PCM method for treating structures in solution. Although both reactions occur with a hydrogen atom transfer, their mechanisms differ from each other by kinetic results. While the reaction of e−aq and H3O+ in solution is diffusion-controlled, NH4+ reacts with e−aq via a transition structure with H-tunneling. The predicted rate constants agree well with available experimental results.
UR - http://www.scopus.com/inward/record.url?scp=85069939625&partnerID=8YFLogxK
U2 - 10.1016/j.cplett.2019.136604
DO - 10.1016/j.cplett.2019.136604
M3 - Article
AN - SCOPUS:85069939625
SN - 0009-2614
VL - 731
JO - Chemical Physics Letters
JF - Chemical Physics Letters
M1 - 136604
ER -