Cope rearrangements in shapeshifting molecules re-examined by means of high-level CCSDT(Q) composite ab initio methods

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Abstract

Benchmark reaction barrier heights for the degenerate Cope rearrangements in the highly fluxional bullvalene and semibullvalene hydrocarbon cages are obtained at the CCSDT(Q) level close to the one-particle basis set limit and include inner-shell, scalar-relativistic, and Born–Oppenheimer corrections. Our best theoretical CCSDT(Q) Gibbs free reaction barrier height for semibullvalene (ΔG298 = 27.9 kJ mol−1) is in good agreement with the most recent experimental value of 25.9 kJ mol−1. However, our CCSDT(Q) reaction barrier height for bullvalene (ΔG298 = 62.2 kJ mol−1) indicates that the most recent gas-phase experimental value of 54.8 ± 0.8 should be revised upward.

Original languageEnglish
Article number138018
JournalChemical Physics Letters
Volume759
DOIs
Publication statusPublished - 16 Nov 2020

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