Can the Counterpoise Correction for Basis Set Superposition Effect Be Justified?

chrinide

JCTC上最近有一篇 反思CP的文章 有理有据 把我之前所想的和想做的全做出来了-- CP是完全没有必要的多此一举

Can the Counterpoise Correction for Basis Set Superposition Effect Be Justified?  
我就懒得翻译了，贴一个ABSTRACT并奉上原文 值得一读 如果哪天 你不想用CP的话或者审稿人Question你没有做CP的时候 就引用这篇文章吧

The basis set superposition efffect (BSSE) is a simple concept, and its validity is
almost universally accepted. So is the counterpoise method to correct for it. The idea is that the
basis set is biased toward the dimer because each monomer in the dimer can “use” the basis
functions on the other monomer, which it cannot in a simple monomer calculation. This
hypothesis can only be tested if basis set free benchmark numbers are available for monomers and
dimer. We are testing the hypothesis on a few systems (in this paper Be2) that are small enough
that sufficiently accurate benchmark numbers (basis set free, or close to basis set limit; full CI or
close to full CI) are available or can be obtained. We find that the answer to the title question is
negative: the standard basis sets of quantum chemistry appear to be biased toward the atom in the
sense that basis set errors are larger for the dimer than the monomer. Applying the counterpoise
correction increases the imbalance by reducing the already smaller basis set error of the monomer
even further. Counterpoise corrected bond energies then deviate more from the basis set limit
numbers than uncorrected bond energies. These conclusions hold both at the HartreeFock level
and (much stronger) at the correlated (CCSD(T), full CI) levels. So the answer to the title
question is No.

wwy0702@126.com

Thanks