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Quantum Monte Carlo investigation of the H-shift and O2-loss channels of cis-2-butene-1-peroxy radical |
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| Authors: | Zhiping Wang Dmitry Yu Zubarev William A Lester Jr |
| Institution: | 2. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA 3. Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA 1. Department of Chemistry, Kenneth S. Pitzer Center for Theoretical Chemistry, University of California, Berkeley, CA, 94720-1460, USA 4. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, 02138, USA |
| Abstract: | Owing to importance in combustion processes, O2-loss and 1, 6-H-shift in cis-2-butene-1-peroxy radical have been investigated. Energies for these processes and the barrier height of the latter are computed using the diffusion Monte Carlo (DMC) method. The DMC energy for the 1, 6-H-shift was determined to be 4.56 ± 0.19 kcal/mol with barrier height of 26.79 ± 0.20 kcal/mol. The energy for O2-loss was found to be 14.93 ± 0.24 kcal/mol. Quantitative differences between the findings of the present study and previous CBS-QB3 results indicate a discrepancy between high-level methods for the resonance-stabilized radicals. Further study is needed to identify the origin of these differences. |
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