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@ARTICLE{Mller:4823,
author = {Müller, T.},
title = {{L}arge-{S}cale {P}arallel {M}ultireference-{A}veraged
{Q}uadratic {C}oupled {C}luster: {T}he {G}round {S}tate of
the {C}hromium {D}imer {R}evisited},
journal = {The journal of physical chemistry / A},
volume = {113},
issn = {1089-5639},
address = {Washington, DC},
publisher = {Soc.},
reportid = {PreJuSER-4823},
pages = {12729 - 12740},
year = {2009},
note = {The calculations have been carried out on the supercomputer
resources provided by the John-von-Neumann Institute for
Computing (NIC) at the Research Centre, Julich. A generous
supply of computing time is gratefully acknowledged. This
work has been partially supported by the European Community
(COST Action D37).},
abstract = {The accurate prediction of the potential energy function of
the X1Sigmag+ state of Cr2 is a remarkable challenge; large
differential electron correlation effects, significant
scalar relativistic contributions, the need for large
flexible basis sets containing g functions, the importance
of semicore valence electron correlation, and its
multireference nature pose considerable obstacles. So far,
the only reasonable successful approaches were based on
multireference perturbation theory (MRPT). Recently, there
was some controversy in the literature about the role of
error compensation and systematic defects of various MRPT
implementations that cannot be easily overcome. A detailed
basis set study of the potential energy function is
presented, adopting a variational method. The method of
choice for this electron-rich target with up to 28
correlated electrons is fully uncontracted
multireference-averaged quadratic coupled cluster (MR-AQCC),
which shares the flexibility of the multireference
configuration interaction (MRCI) approach and is, in
addition, approximately size-extensive (0.02 eV in error as
compared to the MRCI value of 1.37 eV for two noninteracting
chromium atoms). The best estimate for De arrives at 1.48 eV
and agrees well with the experimental data of 1.47 +/- 0.056
eV. At the estimated CBS limit, the equilibrium bond
distance (1.685 A) and vibrational frequency (459 cm-1) are
in agreement with experiment (1.679 A, 481 cm-1). Large
basis sets and reference configuration spaces invariably
result in huge wave function expansions (here, up to 2.8
billion configuration state functions), and efficient
parallel implementations of the method are crucial. Hence,
relevant details on implementation and general performance
of the parallel program code are discussed as well.},
keywords = {J (WoSType)},
cin = {JSC},
ddc = {530},
cid = {I:(DE-Juel1)JSC-20090406},
pnm = {Scientific Computing},
pid = {G:(DE-Juel1)FUEK411},
shelfmark = {Chemistry, Physical / Physics, Atomic, Molecular $\&$
Chemical},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:19725509},
UT = {WOS:000271428100050},
doi = {10.1021/jp905254u},
url = {https://juser.fz-juelich.de/record/4823},
}