Assessment of W1 and W2 theories for the computation of electron affinities, ionization potentials, heats of formation, and proton affinities
S. Parthiban, Jan M. L. Martin
备注：
Journal of Chemical Physics, in press (303115JCP). 2 RevTeX files, first is text and tables, second is E-PAPS tables S-1 through S-5. Additional supplementary material (total energies, basis function exponents) available at http://theochem.weizmann.ac.il/web/papers/w1w2.html
本文介绍了两种新的{ \em ab initio}计算热化学方法，W1和W2理论[J.M.L. Martin和G. de Oliveira，J.Chem.Phys.111，1843（1999）]，评估了由G2-1和G2-2集合中的电离势和电子亲合势以及G2 -1和G2 -2集合的子集中的生成热组成的热化学数据的放大样本。我们发现W1理论对于电离势和电子亲合势的精确度比常用的（并且更便宜的）计算热化学方案（如G2，G3和CBS-QB 3）高出几倍：W2理论对于电子亲合势略有改善，但对于电离势没有显著改善。使用两点的$A+B/L^5$，而不是一个三点的$A+B/C^L$外推的SCF组件大大提高了数值稳定性的W1方法的系统与缓慢的基组收敛。包含一阶自旋轨道耦合对于精确的电离势和涉及简并电子态的电子亲合势是必不可少的：内壳层相关对于电离势比电子亲合势更重要，而标量相对论效应则需要最高的精度。G2-1生成热与实验的平均偏差在平均实验不确定度范围内。W1理论似乎是一个有价值的工具，获得基准质量的质子亲和力。
英文摘要：
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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