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

Misako Aida, Hiroshi Yamataka, Michel Dupuis

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17 Citations (Scopus)

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 languageEnglish
Pages (from-to)262-271
Number of pages10
JournalTheoretical Chemistry Accounts
Volume102
Issue number1-6
Publication statusPublished - 1999

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Methyl Chloride
methyl chloride
hydrolysis
Hydrolysis
prototypes
Trajectories
trajectories
Proton transfer
Molecules
Water
water
molecules
simulation
protons
F region
Interfacial energy
surface energy
Methanol
Molecular dynamics
solutes

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

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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.",
keywords = "Ab initio molecular dynamics, Hydrolysis, Intrinsic reaction coordinate, Methyl chloride, Proton transfer, Solvent effect",
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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.

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KW - Solvent effect

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