Cyanovinyl radical: an illustration of the poor performance of unrestricted perturbation theory and density functional theory procedures in calculating radical stabilization energies |
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Authors: | Christopher J Parkinson Paul M Mayer Leo Radom |
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Institution: | (1) Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia, AU |
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Abstract: | Stabilization energies for the 1-cyanovinyl radical (CH2=CCN) have been calculated using a variety of conventional ab initio (M?ller–Plesset, quadratic configuration interaction
and coupled-cluster) and density functional theory (B-LYP, B3-LYP) procedures, as well as with a range of compound methods.
Compared with a high-level benchmark value (that predicts a stabilization energy of 17.1 kJ mol−1), UMP2 and UMP4 give the wrong sign and magnitude of the stabilization energy (both methods predicting desta- bilization
instead of stabilization), while B-LYP and B3-LYP overestimate the degree of stabilization. The RMP2, RMP4, QCISD(T) and CCSD(T)
techniques, and several, but not all, variants of G2 and CBS theories give radical stabilization energies in good agreement
with the benchmark value.
Received: 15 June 1998 / Accepted: 19 August 1998 / Published online: 15 February 1999 |
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Keywords: | : Radical stabilization energy Spin contamination Unrestricted perturbation theory Density functional theory |
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