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@ARTICLE{Mai:172531,
author = {Mai, Sebastian and Mueller, Thomas and Plasser, Felix and
Marquetand, Philipp and Lischka, Hans and González,
Leticia},
title = {{P}erturbational treatment of spin-orbit coupling for
generally applicable high-level multi-reference methods},
journal = {The journal of chemical physics},
volume = {141},
number = {7},
issn = {1089-7690},
address = {Melville, NY},
publisher = {American Institute of Physics},
reportid = {FZJ-2014-05996},
pages = {074105},
year = {2014},
abstract = {An efficient perturbational treatment of spin-orbit
coupling within the framework of high-level multireference
techniques has been implemented in the most recent version
of the COLUMBUS quantum chemistry package, extending the
existing fully variational two-component (2c)
multi-reference configuration interaction singles and
doubles (MRCISD) method. The proposed scheme follows related
implementations of quasi-degenerate perturbation theory
(QDPT) model space techniques. Our model space is built
either from uncontracted, large-scale scalar relativistic
MRCISD wavefunctions or based on the scalar-relativistic
solutions of the linear-response-theory-based
multi-configurational averaged quadratic coupled cluster
method (LRT-MRAQCC). The latter approach allows for a
consistent, approximatively size-consistent and
size-extensive treatment of spin-orbit coupling. The
approach is described in detail and compared to a number of
related techniques. The inherent accuracy of the QDPT
approach is validated by comparing cuts of the potential
energy surfaces of acrolein and its S, Se, and Te analoga
with the corresponding data obtained from matching fully
variational spin-orbit MRCISD calculations. The conceptual
availability of approximate analytic gradients with respect
to geometrical displacements is an attractive feature of the
2c-QDPT-MRCISD and 2c-QDPT-LRT-MRAQCC methods for structure
optimization and ab inito molecular dynamics simulations},
cin = {JSC},
ddc = {540},
cid = {I:(DE-Juel1)JSC-20090406},
pnm = {411 - Computational Science and Mathematical Methods
(POF2-411)},
pid = {G:(DE-HGF)POF2-411},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000340714600008},
pubmed = {pmid:25149773},
doi = {10.1063/1.4892060},
url = {https://juser.fz-juelich.de/record/172531},
}