Why do variational electron-correlation methods such as truncated configuration-interaction methods tend to be non-size-consistent (non-size-extensive)? Why are size-consistent (size-extensive) methods such as Møller–Plesset perturbation and coupled-cluster methods non-variational? We conjecture that the variational and size-consistent properties are mutually exclusive in an ab initio electron-correlation method (which thus excludes the Hartree–Fock and density-functional methods). We analyze some key examples that support the truth of this conjecture.
%0 Journal Article
%1 noKey
%A Hirata, So
%A Grabowski, Ireneusz
%D 2014
%I Springer Berlin Heidelberg
%J Theoretical Chemistry Accounts
%K chemistry cluster configuration consistent correlation coupled electron interaction quantum size theory unread variational
%N 3
%P 1-9
%R 10.1007/s00214-013-1440-y
%T On the mutual exclusion of variationality and size consistency
%U http://dx.doi.org/10.1007/s00214-013-1440-y
%V 133
%X Why do variational electron-correlation methods such as truncated configuration-interaction methods tend to be non-size-consistent (non-size-extensive)? Why are size-consistent (size-extensive) methods such as Møller–Plesset perturbation and coupled-cluster methods non-variational? We conjecture that the variational and size-consistent properties are mutually exclusive in an ab initio electron-correlation method (which thus excludes the Hartree–Fock and density-functional methods). We analyze some key examples that support the truth of this conjecture.
@article{noKey,
abstract = {Why do variational electron-correlation methods such as truncated configuration-interaction methods tend to be non-size-consistent (non-size-extensive)? Why are size-consistent (size-extensive) methods such as Møller–Plesset perturbation and coupled-cluster methods non-variational? We conjecture that the variational and size-consistent properties are mutually exclusive in an ab initio electron-correlation method (which thus excludes the Hartree–Fock and density-functional methods). We analyze some key examples that support the truth of this conjecture.},
added-at = {2014-02-28T16:47:39.000+0100},
author = {Hirata, So and Grabowski, Ireneusz},
biburl = {https://www.bibsonomy.org/bibtex/25af5c0363ed204a5827d65355f3d1e5c/drmatusek},
doi = {10.1007/s00214-013-1440-y},
interhash = {c218dcdae7446fef0d34b222d18e15b0},
intrahash = {5af5c0363ed204a5827d65355f3d1e5c},
issn = {1432-881X},
journal = {Theoretical Chemistry Accounts},
keywords = {chemistry cluster configuration consistent correlation coupled electron interaction quantum size theory unread variational},
language = {English},
month = mar,
number = 3,
pages = {1-9},
publisher = {Springer Berlin Heidelberg},
timestamp = {2014-02-28T16:47:39.000+0100},
title = {On the mutual exclusion of variationality and size consistency},
url = {http://dx.doi.org/10.1007/s00214-013-1440-y},
volume = 133,
year = 2014
}