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O + C2H4 potential energy surface: lowest-lying singlet at the multireference level

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Abstract

In previous studies (West et al. in J Phys Chem A 113(45):12663, 2009; West et al. in Theor Chem Acc 131:1123, 2012), the lowest-lying O(3P) + C2H4 and singlet PES near the ·CH2CH2O· biradical were extensively explored at several levels of theory. In this work, the lowest-lying O(1D) + C2H4 PES is further examined at the multiconfigurational self-consistent field (MCSCF), MRMP2, CR-CC(2,3), GVB-PP, and MR-AQCC levels. This study aims to provide a detailed comparison of these different levels of theory for this particular system. In particular, many reactions for this system involve multiple bond rearrangements and require various degrees of both non-dynamic and dynamic correlation for reasonable energetics. As a result of this variety, coupled cluster results parallel but do not always match up with multireference results as previously anticipated. In the case of the CH2CHOH → oxirane pathway, MCSCF results show the possibility of a two-step mechanism rather than an elementary step, but the case is very difficult to elucidate. In the case of the CH3C:–OH → H2CCO + H2 pathway, a non-traditional NEB MEP at the GVB-PP level and MR-AQCC stationary point determination illustrate the need for a complex treatment of this surface.

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Acknowledgments

The authors are indebted to Michael W. Schmidt and Mark S. Gordon for help in using the capabilities of GAMESS and MCSCF. This material is based upon work supported by the National Science Foundation under Grant No. OISE-0730114 for the Partnerships in International Research and Education (PIRE) and by the Robert A. Welch Foundation under Grant No. D-0005. TeraGrid resources were provided by the Texas Advanced Computing Center (TACC). Support was also provided by the High-Performance Computing Center (HPCC) at Texas Tech University, under the direction of Philip W. Smith. In addition, this work was supported by the Austrian Science Fund within the framework of the Special Research Program F41 (Vienna Computational Materials Laboratory (ViCoM)). Computer time at the Vienna Scientific Cluster (project no. 70019) is gratefully acknowledged. TLW acknowledges computing resources purchased through funds provided by Ames Laboratory and Iowa State University.

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Authors and Affiliations

  1. Department of Chemistry, Iowa State University, Ames, IA, 50011, USA

    Aaron C. West & Theresa L. Windus

  2. Robert C. Byrd Health Sciences Center, School of Medicine, P.O. Box 9100, Morgantown, WV, 26506-9600, USA

    Joseph D. Lynch

  3. Institute for Theoretical Chemistry, University of Vienna, Waehringerstrasse 17, 1090, Vienna, Austria

    Bernhard Sellner & Hans Lischka

  4. Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, Richland, WA, 99354, USA

    Bernhard Sellner

  5. Department of Chemistry and Biochemistry, Texas Tech University, Memorial Circle and Boston, Lubbock, TX, 79409-1061, USA

    Hans Lischka & William L. Hase

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  1. Aaron C. West
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  2. Joseph D. Lynch
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Correspondence to Theresa L. Windus.

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214_2012_1279_MOESM1_ESM.doc

Additional information including the CAS, CR-CC(2,3), GVB-PP, and MR-AQCC geometries, absolute energies, frequencies, ZPE, moments of inertia, and absolute MRMP2 energies along with plots of CASSCF MEPs with single-point MRMP2 and CR-CC(2,3) energies are available free of charge via the Internet at http://pubs.acs.org. (DOC 3375 kb)

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West, A.C., Lynch, J.D., Sellner, B. et al. O + C2H4 potential energy surface: lowest-lying singlet at the multireference level. Theor Chem Acc 131, 1279 (2012). https://doi.org/10.1007/s00214-012-1279-7

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