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Own N-layered integrated molecular orbital and molecular mechanics study of the reaction of OH− with polychlorinated hydrocarbons CH(4−n)Cln (n=2–4)

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Abstract.

The reliability of the two-layer own N-layered integrated molecular orbital and molecular mechanics (ONIOM) method was examined for the SN2 reaction CH (4−n) Cl n +OH−. In the ONIOM calculation, only the methyl chloride and OH−were treated at a high level and the effect of polychlorination was taken into account only at a low level. The ONIOM results were compared with the “target” CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ results obtained by Borisov etal. [(2001) J. Phys. Chem. A 105:7724]. The ONIOM[MP2/aug-cc-pVDZ:B3LYP/6-31+G(d)] was found to reproduce well the target geometry and energy at the MP2/aug-cc-pVDZ level. The single-point improved energetics at the ONIOM[CCSD(T)/aug-cc-pVDZ:MP2/6-31+G(d)] is found to give results nearly as accurate as the target CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ results. The substantially reduced cost, 20% for optimization and 5% for single-point improved energy of the target cost for n=4, as well as small errors suggest that ONIOM is a powerful tool for accurate potential-energy surfaces of the reaction of large polyhalohydrocarbons.

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Acknowledgments.

The authors are grateful to Bruce Garrett and Yurii Borisov for providing the unpublished results of their ab initio calculations. They are also grateful to Yoshihiro Osamura for some discussions and encouragement. The present research was in part supported by grants (CHE-9627775 and CHE-0209660) from the National Science Foundation. S.R. acknowledges a research fellowship from the Japan Society for Promotion of Sciences. The generous support of computing time at the Emerson Center of Emory University is acknowledged. K.M. also acknowledges the computer time made available at the Molecular Science Computing Facility, Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory.

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Authors and Affiliations

  1. Cherry Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322, USA

    Suyong Re & Keiji Morokuma

  2. Department of Theoretical Studies, Institute for Molecular Science, 444-8585, Japan

    Suyong Re

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  1. Suyong Re
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  2. Keiji Morokuma
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Correspondence to Keiji Morokuma.

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Re, S., Morokuma, K. Own N-layered integrated molecular orbital and molecular mechanics study of the reaction of OH− with polychlorinated hydrocarbons CH(4−n)Cln (n=2–4). Theor Chem Acc 112, 59–67 (2004). https://doi.org/10.1007/s00214-003-0554-z

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  • DOI: https://doi.org/10.1007/s00214-003-0554-z

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