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@ARTICLE{Theophilou:153256,
author = {Theophilou, Iris and Tassi, M. and Thanos, S.},
title = {{C}harge transfer excitations from excited state
{H}artree-{F}ock subsequent minimization scheme},
journal = {The journal of chemical physics},
volume = {140},
number = {16},
issn = {1089-7690},
address = {Melville, NY},
publisher = {American Institute of Physics},
reportid = {FZJ-2014-02906},
pages = {164102},
year = {2014},
abstract = {Photoinduced charge-transfer processes play a key role for
novel photovoltaic phenomena and devices. Thus, the
development of ab initiomethods that allow for an accurate
and computationally inexpensive treatment of charge-transfer
excitations is a topic that nowadays attracts a lot of
scientific attention. In this paper we extend an approach
recently introduced for the description of single and double
excitations[M. Tassi, I. Theophilou, and S. Thanos, Int. J.
Quantum Chem.113, 690 (2013); M. Tassi, I. Theophilou, and
S. Thanos, J. Chem. Phys.138, 124107 (2013)] to allow for
the description of intermolecular charge-transfer
excitations. We describe an excitation where an electron is
transferred from a donor system to an acceptor one, keeping
the excited state orthogonal to the ground state and
avoiding variational collapse. These conditions are achieved
by decomposing the space spanned by the Hartree-Fock (HF)
ground state orbitals into four subspaces: The subspace
spanned by the occupied orbitals that are localized in the
region of the donor molecule, the corresponding for the
acceptor ones and two more subspaces containing the virtual
orbitals that are localized in the neighborhood of the donor
and the acceptor, respectively. Next, we create a Slater
determinant with a hole in the subspace of occupied orbitals
of the donor and a particle in the virtual subspace of the
acceptor. Subsequently we optimize both the hole and the
particle by minimizing the HF energy functional in the
corresponding subspaces. Finally, we test our approach by
calculating the lowest charge-transfer excitation energies
for a set of tetracyanoethylene-hydrocarbon complexes that
have been used earlier as a test set for such kind of
excitations},
cin = {PGI-1 / IAS-1},
ddc = {540},
cid = {I:(DE-Juel1)PGI-1-20110106 / I:(DE-Juel1)IAS-1-20090406},
pnm = {424 - Exploratory materials and phenomena (POF2-424)},
pid = {G:(DE-HGF)POF2-424},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000336047700009},
pubmed = {pmid:24784248},
doi = {10.1063/1.4871502},
url = {https://juser.fz-juelich.de/record/153256},
}