TY - JOUR
T1 - Stationary points for the OH- + CH3F → CH3OH + F- potential energy surface
AU - Sun, Lipeng
AU - Song, Kihyung
AU - Hase, William L.
AU - Sena, Marcelo
AU - Riveros, Jose M.
N1 - Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.
PY - 2003/7/1
Y1 - 2003/7/1
N2 - Ab initio calculations at the HF, MP2, and CCSD(T) levels of theory, utilizing a range of basis sets including the large bases 6-311++G(2df,2pd) and aug-cc-pVTZ, are used to study the OH-+CH3F→CH3OH+F- potential energy surface (PES). Structures, vibrational frequencies, and energies are determined for the reactant and product asymptotic limits, the OH⋯CH3F ion-dipole potential minimum, the [OH⋯CH3⋯F]- central barrier, and the CH3OH⋯F- hydrogen-bonded minimum. This PES does not have a post-reaction F-⋯CH3OH minimum complementary to the pre-reaction OH-⋯CH3F minimum. Except for the CH3OH⋯F- minimum, the large basis sets and MP2 theory give a consistent set of structures and frequencies for the stationary points. Neither the structure nor the vibrational frequencies of the CH3OH⋯F- minimum are converged by the MP2 and large basis set calculations. RHF theory does not describe the energy of the [OH⋯CH3⋯F]- central barrier nor the reaction exothermicity, however, it does give OH-+CH3F→OH-⋯CH3F and F-+CH3OH→CH3OH⋯F- well depths in good agreement with the CCSD(T) values. Overall good agreement is found between the MP2/6-31+G* and much higher level CCSD(T) energies for the stationary points. The MP2 and CCSD(T) calculations give a reaction exothermicity and F-+CH3OH→CH3OH⋯F- well depth in good agreement with the experimental values.
AB - Ab initio calculations at the HF, MP2, and CCSD(T) levels of theory, utilizing a range of basis sets including the large bases 6-311++G(2df,2pd) and aug-cc-pVTZ, are used to study the OH-+CH3F→CH3OH+F- potential energy surface (PES). Structures, vibrational frequencies, and energies are determined for the reactant and product asymptotic limits, the OH⋯CH3F ion-dipole potential minimum, the [OH⋯CH3⋯F]- central barrier, and the CH3OH⋯F- hydrogen-bonded minimum. This PES does not have a post-reaction F-⋯CH3OH minimum complementary to the pre-reaction OH-⋯CH3F minimum. Except for the CH3OH⋯F- minimum, the large basis sets and MP2 theory give a consistent set of structures and frequencies for the stationary points. Neither the structure nor the vibrational frequencies of the CH3OH⋯F- minimum are converged by the MP2 and large basis set calculations. RHF theory does not describe the energy of the [OH⋯CH3⋯F]- central barrier nor the reaction exothermicity, however, it does give OH-+CH3F→OH-⋯CH3F and F-+CH3OH→CH3OH⋯F- well depths in good agreement with the CCSD(T) values. Overall good agreement is found between the MP2/6-31+G* and much higher level CCSD(T) energies for the stationary points. The MP2 and CCSD(T) calculations give a reaction exothermicity and F-+CH3OH→CH3OH⋯F- well depth in good agreement with the experimental values.
KW - Ion-dipole potential
KW - Potential energy surface
KW - S2 reactions
UR - http://www.scopus.com/inward/record.url?scp=0038517900&partnerID=8YFLogxK
U2 - 10.1016/S1387-3806(03)00096-4
DO - 10.1016/S1387-3806(03)00096-4
M3 - Article
AN - SCOPUS:0038517900
VL - 227
SP - 315
EP - 325
JO - International Journal of Mass Spectrometry
JF - International Journal of Mass Spectrometry
SN - 1387-3806
IS - 3
ER -