Unusual Inorganic Biradicals: A Theoretical Analysis

Authors

  • Dr. Evangelos Miliordos,

    1. Physical Sciences Division, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, MS K1-83, Richland, WA 99352 (USA)
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  • Prof. Klaus Ruedenberg,

    1. Department of Chemistry and Ames Laboratory USDOE, Iowa State University, Ames, IA 50011 (USA)
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  • Dr. Sotiris S. Xantheas

    Corresponding author
    1. Physical Sciences Division, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, MS K1-83, Richland, WA 99352 (USA)
    • Physical Sciences Division, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, MS K1-83, Richland, WA 99352 (USA)

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  • This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences at Pacific Northwest National Laboratory (PNNL), a multiprogram national laboratory operated for the DOE by Battelle (for E.M. and S.S.X.) and at Iowa State University under Contract No. DE-AC02-07CH11358 through the Ames Laboratory (for K.R.). This research used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Abstract

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The biradical character β (1 for an ideal biradical) is determined from multi-reference configuration interaction (MRCI) wavefunctions. Triatomics in the series FX2+ (X=O, S, Se, Te, Po) exhibit unusually high biradical characters for X=Te, Po (0.76<β<0.92), the largest among the homologous 18 valence electron molecules CX22−, NX2, X3, and OX2. On the same scale, the biradical character of O3 is just 0.19, whereas that of C(CH2)3 is 0.97.

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