error in bond dissociation energy of gas phase molecule

Jun chen... at gmail.com
Thu Apr 7 19:03:33 CEST 2011


Thanks for the comments.

> I remember a similar case where the production of a spin polarized
> intermediate resulted in a "wrong" activation energy. The problem
> was related (at that time) to the carbon pseudopotential
> that had bad transferability from non-spin-polarized to
> spin-polarized situations. This could be a similar situation.

If it is the case, the problem seems serious. Is it possible that the
problem is less serious in condensed phases?

> BTW check the literature for the really bad behavior of all
> non SIE corrected functionals for this type of reaction.

We are comparing the computed bond dissociation energies for the same
functional, other than with experiments. Or, am I misunderstanding
anything? B3LYP gives rather satisfactory value, while BLYP value is
too large. Our gpw calculations always give values about 0.5 eV lower
than gapw, gaussian and literature results.

Jun



More information about the CP2K-user mailing list