Quantum Monte Carlo study of the reaction [electronic resource] : C1 + CH3OH -->CH2OH+ HCl
- Washington, D.C. : United States. Dept. of Energy, 2003.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
- Additional Creators:
- United States. Department of Energy
United States. Department of Energy. Office of Scientific and Technical Information
- A theoretical study is reported of the Cl + CH₃OH → CH₂OH + HCl reaction based on the diffusion Monte Carlo (DMC) variant of the quantum Monte Carlo method. Using a DMC trial function constructed as a product of Hartree-Fock and correlation functions, we have computed the barrier height, heat of reaction, atomization energies and heats of formation of reagents and products. The DMC heat of reaction, atomization energies, and heats of formation are found to agree with experiment to within the error bounds of computation and experiment. Moller-Plesset second order perturbation theory (MP2) and density functional theory, the latter in the B3LYP generalized gradient approximation, are found to overestimate the experimental heat of reaction. Intrinsic reaction coordinate calculations at the MP2 level of theory demonstrate that the reaction is predominantly direct, i.e., proceeds without formation of intermediates, which is consistent with a recent molecular beam experiment. The reaction barrier as determined from MP2 calculations is found to be 2.24 kcal/mol and by DMC it is computed to be 2.39(49) kcal/mol.
- Published through SciTech Connect.
Journal of Chemical Physics 121 3 ISSN 0021-9606; JCPSA6 FT
Kollias, A.C.; Lester Jr., W.A.; Couronne, O.
Ernest Orlando Lawrence Berkeley NationalLaboratory, Berkeley, CA (US)
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