TY - JOUR
T1 - The F-+CH3I → FCH3 +I- entrance channel potential energy surface Comparison of electronic structure methods
AU - Sun, Rui
AU - Xie, Jing
AU - Zhang, Jiaxu
AU - Hase, William L.
PY - 2015
Y1 - 2015
N2 - The potential energy surface (PES) of the F- + CH3I → FCH3 +I- Sn2 nucleophilic substitution reaction has been studied previously using MP2 and DFT levels of theory (J. Phys. Chem. A 2010,114,9635-9643). This work indicated that DFT gives a better representation of the PES which has only an hydrogen-bonded entrance channel reaction path, with a hydrogen-bonded transition state [F··HCH2··I]- connecting the hydrogen-bonded pre-reaction complex F-··· HCH2I and C3v post-reaction complex FCH3··· I-. For the work presented here, CCSD(T) with three different basis set and two effective core potentials (i.e. PP/d, PP/t and ECP/d) was employed to investigate stationary point properties for this reaction. Besides the hydrogen-bonded entrance channel stationary points, CCSD(T) also predicts a traditional C3v transition state [F··CH3·· I]- connecting a C3v pre-reaction complex F-·· CH3I with the C3v post-reaction complex FCH3 · · ·I-. Though CCSD(T) gives a CH3F···I- binding energy and CH3 F and CH3I geometries in almost exact agreement with experiment, it gives a heat of reaction ∼20 kJ/mol less exothermic than experiment. The MP2 PES for this reaction, determined in the previous study, is very similar to the CCSD(T), but obtained with a much smaller computational cost. Direct dynamics simulations for the F- + CH3I→ FCH3 +I- reaction are feasible with MP2.
AB - The potential energy surface (PES) of the F- + CH3I → FCH3 +I- Sn2 nucleophilic substitution reaction has been studied previously using MP2 and DFT levels of theory (J. Phys. Chem. A 2010,114,9635-9643). This work indicated that DFT gives a better representation of the PES which has only an hydrogen-bonded entrance channel reaction path, with a hydrogen-bonded transition state [F··HCH2··I]- connecting the hydrogen-bonded pre-reaction complex F-··· HCH2I and C3v post-reaction complex FCH3··· I-. For the work presented here, CCSD(T) with three different basis set and two effective core potentials (i.e. PP/d, PP/t and ECP/d) was employed to investigate stationary point properties for this reaction. Besides the hydrogen-bonded entrance channel stationary points, CCSD(T) also predicts a traditional C3v transition state [F··CH3·· I]- connecting a C3v pre-reaction complex F-·· CH3I with the C3v post-reaction complex FCH3 · · ·I-. Though CCSD(T) gives a CH3F···I- binding energy and CH3 F and CH3I geometries in almost exact agreement with experiment, it gives a heat of reaction ∼20 kJ/mol less exothermic than experiment. The MP2 PES for this reaction, determined in the previous study, is very similar to the CCSD(T), but obtained with a much smaller computational cost. Direct dynamics simulations for the F- + CH3I→ FCH3 +I- reaction are feasible with MP2.
KW - Ion
KW - Molecular dynamics simulation
KW - Nucleophilic substitution reaction
UR - http://www.scopus.com/inward/record.url?scp=84936865373&partnerID=8YFLogxK
U2 - 10.1016/j.ijms.2014.04.006
DO - 10.1016/j.ijms.2014.04.006
M3 - Article
AN - SCOPUS:84936865373
VL - 377
SP - 222
EP - 227
JO - International Journal of Mass Spectrometry
JF - International Journal of Mass Spectrometry
SN - 1387-3806
IS - 1
ER -