Assessment of W1 and W2 theories for the computation of electron affinities, ionization potentials, heats of formation, and proton affinities

Details Assessment of W1 and W2 theories for the computation of electron affinities, ionization potentials, heats of formation, and proton affinities Assessment of W1 and W2 theories for the computation of electron affinities, ionization potentials, heats of formation, and proton affinities

2001-01-17

arxiv.org/abs/physics/0101072v2

J. Chem. Phys. 114, 6014-6029 (2001)

Physics

Chemical Physics

Journal of Chemical Physics, in press (303115JCP). 2 RevTeX files, first is text and tables, second is E-PAPS tables S-1 throu

Scientific paper

10.1063/1.1356014

The performance of two recent {\em ab initio} computational thermochemistry schemes, W1 and W2 theory [J.M.L. Martin and G. de Oliveira, J. Chem. Phys. 111, 1843 (1999}], is assessed for an enlarged sample of thermochemical data consisting of the ionization potentials and electron affinities in the G2-1 and G2-2 sets, as well as the heats of formation in the G2-1 and a subset of the G2-2 set. We find W1 theory to be several times more accurate for ionization potentials and electron affinities than commonly used (and less expensive) computational thermochemistry schemes such as G2, G3, and CBS-QB3: W2 theory represents a slight improvement for electron affinities but no significant one for ionization potentials. The use of a two-point $A+B/L^5$ rather than a three-point $A+B/C^L$ extrapolation for the SCF component greatly enhances the numerical stability of the W1 method for systems with slow basis set convergence. Inclusion of first-order spin-orbit coupling is essential for accurate ionization potentials and electron affinities involving degenerate electronic states: inner-shell correlation is somewhat more important for ionization potentials than for electron affinities, while scalar relativistic effects are required for the highest accuracy. The mean deviation from experiment for the G2-1 heats of formation is within the average experimental uncertainty. W1 theory appears to be a valuable tool for obtaining benchmark quality proton affinities.

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