Publication: Isomerization energies of tetrahedranes to 1,3-cyclobutadienes: A challenge for theoretical methods

All || By Area || By Year

Title	Isomerization energies of tetrahedranes to 1,3-cyclobutadienes: A challenge for theoretical methods
Authors/Editors*	S Rayne, K Forest
Where published*	Computational and Theoretical Chemistry
How published*	Journal
Year*	2012
Volume	979
Number	1
Pages	1-9
Publisher	Elsevier
Keywords	Tetrahedranes; 1,3-Cylobutadienes; Isomerization energies; Theoretical methods
Link	http://dx.doi.org/10.1016/j.comptc.2011.10.017
Abstract	The gas phase (298.15 K, 1 atm) isomerization energies (ÎisomE(g)) of various tetra-substituted (hydro, chloro, bromo, methyl, ethynyl, cyano, tert-butyl, and tetrakis(trimethylsilyl)) tetrahedranes to their corresponding 1,3-cyclobutadienes were investigated with a broad range of model chemistries (Hartree-Fock, density functional, Moller-Plesset perturbation, composite, coupled cluster, and quadratic configuration interaction methods) and Pople-/Ahlrichs-/Dunning-type basis sets. Substantial model chemistry dependent ÎisomE(g) variability was found for all tetrahedrane/1,3-cyclobutadiene derivatives. Basis set influences on ÎisomE(g) variability were modest and less influential than the choice of model chemistry. Several density functionals previously found to provide excellent ÎisomE(g) prediction performance for a broad range of small and large organic compounds demonstrated poor capability when applied to the tetrahedrane/1,3-cyclobutadiene isomerizations.