Abstract
Ab initio molecular dynamics simulations at the Hartree-Fock/6-31G level of theory are performed on methyl chloride hydrolysis with explicit consideration of one solute and two solvent water molecules at a temperature of 298 K. The reaction involves the formation of a reactant complex and the energy surface to the transition state is found to be simple. Two types of trajectories toward the product are observed. In the first type, the system reaches an intermediate complex (complex-P1) region after two nearly concerted proton transfers involving the attacking water molecule and the solvent water molecules. These trajectories resemble the intrinsic reaction coordinate trajectory. The thermal motion of the atoms leads the system to another intermediate complex (complex-P2) region. A second type of trajectory is found in which the system reaches the complex-P2 region directly after the proton transfers. In both of these forward trajectories, back proton transfers lead the system to a final complex-F region which resembles protonated methanol.
| Original language | English |
|---|---|
| Pages (from-to) | 262-271 |
| Number of pages | 10 |
| Journal | Theoretical Chemistry Accounts |
| Volume | 102 |
| Issue number | 1-6 |
| Publication status | Published - 1999 |
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Keywords
- Ab initio molecular dynamics
- Hydrolysis
- Intrinsic reaction coordinate
- Methyl chloride
- Proton transfer
- Solvent effect
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
Cite this
Ab initio MD simulations of a prototype of methyl chloride hydrolysis with explicit consideration of three water molecules : A comparison of MD trajectories with the IRC path. / Aida, Misako; Yamataka, Hiroshi; Dupuis, Michel.
In: Theoretical Chemistry Accounts, Vol. 102, No. 1-6, 1999, p. 262-271.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Ab initio MD simulations of a prototype of methyl chloride hydrolysis with explicit consideration of three water molecules
T2 - A comparison of MD trajectories with the IRC path
AU - Aida, Misako
AU - Yamataka, Hiroshi
AU - Dupuis, Michel
PY - 1999
Y1 - 1999
N2 - Ab initio molecular dynamics simulations at the Hartree-Fock/6-31G level of theory are performed on methyl chloride hydrolysis with explicit consideration of one solute and two solvent water molecules at a temperature of 298 K. The reaction involves the formation of a reactant complex and the energy surface to the transition state is found to be simple. Two types of trajectories toward the product are observed. In the first type, the system reaches an intermediate complex (complex-P1) region after two nearly concerted proton transfers involving the attacking water molecule and the solvent water molecules. These trajectories resemble the intrinsic reaction coordinate trajectory. The thermal motion of the atoms leads the system to another intermediate complex (complex-P2) region. A second type of trajectory is found in which the system reaches the complex-P2 region directly after the proton transfers. In both of these forward trajectories, back proton transfers lead the system to a final complex-F region which resembles protonated methanol.
AB - Ab initio molecular dynamics simulations at the Hartree-Fock/6-31G level of theory are performed on methyl chloride hydrolysis with explicit consideration of one solute and two solvent water molecules at a temperature of 298 K. The reaction involves the formation of a reactant complex and the energy surface to the transition state is found to be simple. Two types of trajectories toward the product are observed. In the first type, the system reaches an intermediate complex (complex-P1) region after two nearly concerted proton transfers involving the attacking water molecule and the solvent water molecules. These trajectories resemble the intrinsic reaction coordinate trajectory. The thermal motion of the atoms leads the system to another intermediate complex (complex-P2) region. A second type of trajectory is found in which the system reaches the complex-P2 region directly after the proton transfers. In both of these forward trajectories, back proton transfers lead the system to a final complex-F region which resembles protonated methanol.
KW - Ab initio molecular dynamics
KW - Hydrolysis
KW - Intrinsic reaction coordinate
KW - Methyl chloride
KW - Proton transfer
KW - Solvent effect
UR - http://www.scopus.com/inward/record.url?scp=84961979626&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84961979626&partnerID=8YFLogxK
M3 - Article
VL - 102
SP - 262
EP - 271
JO - Theoretical Chemistry Accounts
JF - Theoretical Chemistry Accounts
SN - 1432-881X
IS - 1-6
ER -