Quantum mechanical size and steric hindrance.
A quantum mechanical definition of molecular size and shape is formulated from the electronic second moment of the Hartree-Fock wave function. The shape tensor is defined to be invariant with respect to the origin. The geometric average of the eigenvalues of the tensor correlates very well with van der Waals and Bragg-Slater radii. There is also a close linear relationship between this definition of molecular size and molecular volumes determined computationally using isodensity contours. Furthermore, this definition of molecular size is effective in predicting the steric effects of substituents, as predicted by existing methods, such as the modified Taft Ee(s), P-values, and n-values.
Hollett
Joshua W
JW
Department of Chemistry, Memorial University of Newfoundland, St. John's, NL A1B 3X7, Canada. jhollett@mun.ca
Kelly
Aaron
A
Poirier
Raymond A
RA