Spin state relaxation of iron complexes: The case for OPBE and S12g
J. Serb. Chem. Soc. 80 (11) 1399–1410 (2015) UDC 546.722/.723+533.6.013.7:
JSCS–4806 532.14:537.872
Original scientific paper
1399
Spin state relaxation of iron complexes:
The case for OPBE and S12g
MAJA GRUDEN1, STEPAN STEPANOVIĆ2# and MARCEL SWART3,4*
1Faculty of Chemistry, University of Belgrade, Studentski trg 12–16, 11001 Belgrade, Serbia,
2Center for Chemistry, ICTM, University of Belgrade, Njegoševa 12, 11001 Belgrade, Serbia,
3Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química,
Universitat de Girona, Campus Montilivi, Facultat de Ciències, 17071 Girona, Spain and
4Institució Catalana de Recerca i Estudis Avançats (ICREA), Pg. Lluís Companys 23,
08010 Barcelona, Spain
(Received 11 June, revised 14 July, accepted 15 July 2015)
Abstract: The structures of nine iron complexes that show a diversity of
experimentally observed spin ground states were optimized and analyzed using
the Density Functional Theory (DFT). An extensive validation study of the
new S12g functional was performed, with a discussion concerning the inf-
luence of the environment, geometry and its overall performance based on a
comparison with the well-proven OPBE functional. The OPBE and S12g func-
tionals gave the correct spin ground state for all investigated iron complexes.
Since S12g performs remarkably well, it could be considered a reliable tool for
studying the energetics of the spin state in complicated transition metal sys-
tems.
Keywords: density functional theory; Fe(II) and Fe(III) coordination com-
pounds; validation study; spin states.
INTRODUCTION
Spin is an intrinsic and inherent property of atoms and molecules.1 Most
transition metal ions with partially filled d-shells can exhibit different kinds of
spin multiplicity in the ground state, i.e., can lead to different spin states.
Depending on the oxidation number, iron complexes usually have either 5 or 6 d-
electrons that can be distributed in an octahedral environment in at least two dif-
ferent ways: with a maximum number of unpaired electrons, leading to the high
spin (HS) state, or with maximally paired electrons – giving the low spin (LS)
state. Other possibilities of the distribution of electrons represent an intermediate
(IS) spin state. Since HS, IS and LS complexes usually display quite different
* Corresponding author. E-mail: marcel.swart@icrea.cat
# Serbian Chemical Society member.
doi: 10.2298/JSC150611068G
1400 GRUDEN, STEPANOVIĆ and SWART
structural, spectral and magnetic properties, and often reactivity, it is of the
utmost importance to have both experimental and theoretical methods to deter-
mine correctly the spin ground state of a system. However, both experiment and
theory have difficulties and problems, and many studies have been devoted to
this issue in the last decade.2–5
From a broad palette of quantum mechanical methods, the density functional
theory (DFT)6–8 has emerged into the mainstream, mainly because it gives a
good compromise between accuracy of the results and computational effici-
ency.9–11 However, although the DFT, in principle, gives an exact energy, a
universal functional is still unknown, leading to density functional approxim-
ations (DFAs). These DFAs are parameterized for different properties and, note-
worthy, spin-state energies were not included in the development for most of
nowadays available DFAs.12 It has been shown that the accuracy of the results
not only strongly depends on the choice of the DFAs, but also on the basis set
that is used.1,3,13,14 Early pure functionals, such as LDA,15–17 BP86,18,19
BLYP,19,20 and PW91,21,22 have a tendency to favor LS states,14 while hybrid
functionals, such as B3LYP,23,24 PBE025 and M06,26,27 systematically favor HS
states.14 For the reliable prediction of the correct spin ground state from a num-
ber of close lying states, OPBE14 has emerged to be one of the best functionals
for the task.28 Recently, Swart constructed a new density functional that com-
bines the best of OPBE (spin states, reaction barriers) with the best of PBE (weak
interactions) into the S12g5 DFA.
Previously, the relative spin state energies of seven iron complexes (1–7,
Fig. 1) on OLYP20,29 optimized geometries (1–3) and on crystal structures (4–7)
with a variety of DFAs were reported, which already showed the good perform-
ance of OPBE for vertical spin state splittings.14
Herein, a detailed DFT study on OPBE optimized geometries of iron
complexes (1–7) with experimentally established spin ground states, ranging
from singlet to sextet, is reported together with an extension to include two iron
porphyrinato complexes (8 and 9, Fig. 1) that were reported to have different
electronic ground states in spite of their similarity.30–32
Furthermore, a comprehensive validation study of the S12g DFA,5 together
with an examination of the influence of the chemical environment, was per-
formed on all the investigated complexes.
METHODOLOGY
All DFT calculations were performed with the Amsterdam Density Functional (ADF)
suite of program.33,34 MOs were expanded in an uncontracted set of Slater type orbitals
(STOs) of triple-ζ quality containing diffuse functions (TZP)35 and one set of polarization
functions. Core electrons (1s for 2nd period and 1s2s2p for 3rd–4th period) were not treated
explicitly during the geometry optimizations (frozen core approximation), as the core was
shown to have a negligible effect on the obtained geometries.36 An auxiliary set of s, p, d, f,
SPIN STATE ENERGETICS OF IRON COMPLEXES 1401
and g STOs was used to fit the molecular density and to represent the Coulomb and exchange
potentials accurately for each self-consistent field (SCF) cycle.
Fig. 1. Fe(PyPepS)2 1 (PyPepSH2 = N-(2-mercaptophenyl)-2′-pyridinecarboxamide);
Fe(tsalen)Cl 2 (tsalen = 2,2′-[1,2-ethanediylbis(nitrilomethylidyne)]bis[benzenethiolato];
Fe(N(CH2-o-C6H4S)3)(1-Me-imidazole) 3; (Fe(NH)S4)L 4 (L=CO), 5 (PMe3), 6 (NH3), 7
(N2H4)((NH)S4 = bis(2-((2-mercaptophenyl)thio)ethyl)amine); iron porphyrin chloride
(8, FePCl) and iron porphyrazine chloride (9, FePzCl).
Energies and gradients were calculated using the OPBE and S12g functionals in the gas
phase and with COSMO (methanol as a solvent)37-39 in the dielectric continuum model for a
solvent environment. The geometries were optimized with the QUILD program40 using
adapted delocalized coordinates41 until the maximum gradient component was less than 10-4
a.u. Subsequent single point calculations that utilize all electron basis set were performed on
all optimized geometries, with OPBE and S12g.
RESULTS AND DISCUSSION
The total set of molecules consists of both Fe(III) (1–3, 8 and 9) and Fe(II)
(4–7) complexes, and show a diversity of experimentally observed spin ground
states. A thorough examination with the OPBE and S12g functionals in the gas
phase and the COSMO solvent environment was performed. The discussion is
1402 GRUDEN, STEPANOVIĆ and SWART
commenced by focusing on the influence of structure relaxation on the spin states
of Fe(III)-complexes 1–3.42 Experimentally, Fe-(PyPepS)2 (1, PyPepSH2 = N-(2-
-mercaptophenyl)-2-pyridinecarboxamide) has a LS doublet ground state,43
Fe(tsalen)Cl (2, tsalen = 2,2′-[1,2-ethanediylbis(nitrilomethylidyne)]bis[ben-
zenethiolato] 2,2′-[1,2-ethanediylbis(nitrilomethylidyne)]bis[benzenethiolato]) an
intermediate spin (IS), quartet ground state44 and Fe(N(CH2-o-C6H4S)3)(1-Me-
imidazole, 3) a HS sextet ground state.45 Then, the Fe(II)-complexes
((Fe(NH)S4)L, (NH)S4 = bis(2-((2-mercaptophenyl)thio)ethyl)amine, L = CO (4),
PMe3 (5), NH3 (6) and N2H4 (7)) are discussed. Compounds 4 and 5 have a LS
(singlet) state and compounds 6 and 7, reportedly, a HS (quintet) ground state.46–48
Furthermore, focus is placed on FeIII(porphyrinato)Cl, FePCl (8) and, FeIII(por-
phyrazinato)Cl, FePzCl (9), which have a sextet and a quartet ground state,
respectively.
Structure relaxation and spin state energies of Fe(III) compounds 1–3
The optimization of the three Fe(III) molecules (1–3) led in all cases to the
expected structural changes for the different spin states (Tables S-I–S-III of the
Supplementary material to this paper). Comparison of the optimized structures of
1–3 indicated the existence of an expansion of the ligand sphere. Going from the
doublet to the quartet state, first the equatorial ligands moved away from iron
while the axial ligands stayed almost at the same position. In the sextet state, the
equatorial ligands remained virtually at the same position, but the axial ligands
(had to) moved out.
Comparing the vertical spin state energies, calculated on the experimental
structure,14 with results from the optimized (“relaxed”) geometries, Table I, it is
evident that the energy gap between different spin states decreased. In the case of
compound 1, the doublet state remained the spin ground state with the quartet
state (from 22.5 kcal*·mol–1 “vertical” to 17.5 kcal·mol–1 “relaxed”) and the
sextet state (from 33.9 kcal·mol–1 “vertical” to 10.2 kcal·mol–1 “relaxed”) in
closer energetic proximity after geometry optimization. Molecule 2 has the quar-
tet ground state, and here, the relative energies of the doublet and sextet states
were reduced after structure relaxation. The same trends apply for the sextet
ground state of complex 3. For all complexes, after spin state relaxation, both
OPBE and its recently developed successor S12g gave the correct spin ground
state. Spin contamination was small for these complexes, and therefore, will not
be discussed further.
The choice of exchange-correlation functional had an obvious influence on
the geometry, with a tendency of S12g to give somewhat longer bond lengths
than OPBE (Tables S-I–S-III). It should be noted that S12g gave structural
parameters that were in excellent agreement with experimental values. Unlike the
* 1 kcal = 4184 J
SPIN STATE ENERGETICS OF IRON COMPLEXES 1403
choice of functional, the influence of solvation on the geometrical parameters
during the structural relaxation was not very significant, and it depended slightly
on the system under consideration. In most cases, optimizations with COSMO
gave slightly longer bonds, but without significant consequences for the spin-
state splittings, Table I.
TABLE I. Spin state energies (kcal mol-1) for Fe(III) molecules 1–3 using TZP basis set, with
OPBE and S12g functionals, in vacuum and COSMO
Geo.a SPb
Fe-(PyPepS)2 1 Fe(tsalen)Cl 2 Fe(N(CH2-o-C6H4S)3)(1MImb) 3
Doublet Quartet Sextet Doublet Quartet Sextet Doublet Quartet Sextet
OPBE OPBE 0 17.1 10.2 6.5 0 3.9 6.6 7.9 0
OPBE
cosmo
0 19.4 13.0 9.3 0 6.9 7.9 7.4 0
S12g 0 15.8 8.7 7.6 0 3.8 6.8 7.2 0
S12g
cosmo
0 18.2 11.6 10.2 0 6.4 8.2 6.8 0
OPBE
cosmo
OPBE 0 18.8 13.1 5.2 0 2.9 6.2 7.5 0
OPBE
cosmo
0 17.4 10.2 9.7 0 7.7 8.0 7.2 0
S12g 0 18.4 13.3 6.0 0 3.0 6.5 6.8 0
S12g
cosmo
0 17.1 10.6 10.2 0 7.4 8.3 6.5 0
S12g OPBE 0 18.3 10.5 7.4 0 6.2 7.6 8.1 0
OPBE
cosmo
0 22.7 14.7 10 0 9.2 8.6 7.1 0
S12g 0 15.4 8.7 7.5 0 6.6 6.5 7.0 0
S12g
cosmo
0 19.9 13.1 9.9 0 9.3 7.7 6.1 0
S12g
cosmo
OPBE 0 17.5 10.6 7.0 0 4.7 7.5 8.4 0
OPBE
cosmo
0 20.5 14.9 11.2 0 6.7 8.8 7.2 0
S12g 0 15.7 9.2 6.6 0 4.7 6.1 6.8 0
S12g
cosmo
0 18.8 13.7 10.4 0 6.5 7.6 5.9 0
aGeometry optimization with frozen core electrons; bsubsequent single point calculations with all-electron basis sets
Structure relaxation and spin state energies of compounds 4–7
The spin state dependent structure relaxation for the Fe(II) compounds
results in similar differences in Fe–ligand distances as for the Fe(III) compounds
(Tables S-IV–S-VII). In the case of compounds 4–7, the Fe–N, Fe–S and Fe–C
distances were slightly elongated in comparison to the distances in the Fe(III)
complexes due to the additional d-electron in the Fe(II) systems.
The spin ground states of the Fe(II) complexes 4 and 5 were correctly
predicted using both the OPBE and S12g levels of theory (see Table II): the
singlet state was the lowest in energy for both molecules, in agreement with expe-
1404 GRUDEN, STEPANOVIĆ and SWART
TABLE II. Spin state energies (kcal mol-1) for labile (trans) complexes 4 and 5 using TZP
basis, with OPBE and S12g functionals, in vacuum and COSMO
Geo.a SPb
trans-(Fe(NH)S4)CO 4 trans-(Fe(NH)S4)PMe3 5
Singlet Triplet Quintet Singlet Triplet Quintet
OPBE OPBE 0 23.4 34.8 0 16.3 20.1
OPBE cosmo 0 24.5 36.6 0 17.3 18.6
S12g 0 19.1 28.0 0 14.5 17.7
S12g cosmo 0 20.2 29.7 0 15.4 16.3
OPBE
cosmo
OPBE 0 23.5 35.3 0 16.4 20.4
OPBE cosmo 0 24.5 36.5 0 17.3 18.3
S12g 0 19.4 29.1 0 15.1 19.1
S12g cosmo 0 20.3 30.3 0 15.9 17.1
S12g OPBE 0 23.4 34.2 0 19.6 19.4
OPBE cosmo 0 24.3 36.4 0 20.3 19.2
S12g 0 18.7 29.3 0 15.6 16.8
S12g cosmo 0 19.6 31.4 0 16.3 16.6
S12g
cosmo
OPBE 0 24.6 35.0 0 19.9 19.2
OPBE cosmo 0 24.8 36.5 0 20.6 18.2
S12g 0 20.4 30.8 0 15.8 17.1
S12g cosmo 0 20.5 32.2 0 16.4 16.2
aGeometry optimization with frozen core electrons; bsubsequent single point calculations with all-electron basis sets
rimental data. For compound 4, the triplet and quintet states were significantly
higher in energy. The energy differences between the different states were
smaller for compound 5. Similar to the Fe(III) complexes, spin contamination
was small and will not be discussed any further. Similar to compounds 4 and 5,
after spin state structure relaxation, an LS ground state for iron complexes 6 and
7 was found, with IS and HS higher in energy. Unfortunately, the experimental
determination of the spin states of compounds 6 and 7 were inconclusive, since
anomalous high μeff values of 10–13 μB were measured that may indicate impur-
ities, e.g., by metallic iron, or oligomer formation. For compound 7 in solution,
an HS state was observed,48 but a compound similar to 7 showed a diamagnetic
LS Fe center.49 Moreover, indications of dimer formation of the ligand-free
[(Fe(NH)S4)] complex were observed.47,48 Since different forms of the
(Fe(NH)S4)L complex in these studies were obtained, both forms for compounds
4–7, i.e., with the “trans” and “meso” form (see Fig. 2) had to be checked. For
both forms of each of compounds 4–7, an LS ground state was found, albeit with
smaller spin-state splitting for compounds 6 and 7. These findings could be
traced back to the strength of the iron–ligand bond, which seems to be much
weaker for compounds 6/7 than for compounds 4/5. The weakly bound NH3 and
N2H4 ligands are easily exchanged with CH3OH, solvent (THF) or CO.48 These
experimental data corroborate the present computed ligand-binding energies,
which indicate strong and favorable binding of CO and P(Me)3 to form the
singlet ground state, but less favorable binding of the other ligands or spin states
SPIN STATE ENERGETICS OF IRON COMPLEXES 1405
(see Table S-VIII of the Supplementary material). Interestingly, the monomeric
Fe(NH)S4 complex without a ligand was predicted to have a triplet spin ground
state in the trans form, with the other spin states or the meso form lying higher in
energy by at least 7 kcal·mol–1. The ligand-free complex may dimerize to give
the experimentally observed HS state through ferromagnetic coupling. The latter
process was not studied due to the complexity involved with ferromagnetic ver-
sus anti-ferromagnetic coupling of the many spin states that need to be con-
sidered. This was confirmed by a recent study using high-level ab initio methods
that indeed found a singlet ground-state for these molecules.50 In another recent
study, “accurate” spin ground states for molecules 6 and 7 were found with the
double hybrid B2PLYP functional, where an HS ground-state was obtained for
molecule 6 with OPBE.51 Since the last result is in disagreement with the results
of the present study, molecules 6 and 7 were re-optimized using the OPBE func-
tional with the geometries from their paper51 as the starting point. The re-opti-
mized structures resulted in spin state splittings that were in accordance with the
previous study,51 however, the structures were highly distorted representing only
a local minimum on the potential energy surface (and ca. 5–20 kcal·mol–1 above
the structures obtained here in Table III).
Fig. 2. Different forms of compounds 4–7.
TABLE III. Spin state energies (kcal mol-1) for labile (meso) complexes 6 and 7 using TZP
basis, with OPBE and S12g functionals, in vacuum and COSMO
Geo.a SPb
meso-(Fe(NH)S4)NH3 (6) meso-(Fe(NH)S4)N2H4 (7)
Singlet Triplet Quintet Singlet Triplet Quintet
OPBE OPBE 0 10.3 6.6 0 11.3 6.6
OPBE cosmo 0 10.1 3.9 0 10.7 4.4
S12g 0 7.7 2.6 0 8.5 2.5
S12g cosmo 0 7.4 –0.1 0 7.9 0.3
OPBE
cosmo
OPBE 0 10.6 7.2 0 11.5 7.1
OPBE cosmo 0 9.9 3.5 0 10.1 3.8
S12g 0 7.9 3.5 0 9.7 3.6
S12g cosmo 0 7.0 –0.2 0 8.2 0.5
1406 GRUDEN, STEPANOVIĆ and SWART
TABLE III. Continued
Geo.a SPb
meso-(Fe(NH)S4)NH3 (6) meso-(Fe(NH)S4)N2H4 (7)
Singlet Triplet Quintet Singlet Triplet Quintet
S12g OPBE 0 10.1 7.5 0 11.1 7.6
OPBE cosmo 0 10.7 5.7 0 11.0 6.8
S12g 0 8.4 5.3 0 9.3 5.3
S12g cosmo 0 8.7 3.4 0 9.2 4.6
S12g
cosmo
OPBE 0 10.1 6.8 0 10.8 6.6
OPBE cosmo 0 10.5 4.4 0 10.4 5.2
S12g 0 8.7 4.9 0 9.4 4.6
S12g cosmo 0 8.8 2.4 0 8.9 3.2
aGeometry optimization with frozen core electrons; bsubsequent single point calculations with all-electron basis sets
As in the case of the previous investigated molecules 1–3, after optimization
with S12g, somewhat longer bond lengths were obtained in comparison with the
OPBE geometries. Nevertheless, both of them are again in good agreement with
the experimental data (Tables S-IV–S-VII). In contrast to the Fe(II) complexes
1–3, the Fe(III) P450 model systems 4–7 are prone to the influence of solvent
(COSMO calculations) on the spin state ordering, Tables II and III. Calculations
with the COSMO solvation model revealed a tendency to favor the HS state for
complexes 5–7, and the LS state for complex 4.
Iron porphyrin chloride and the porphyrazine analogue
The structures of FePCl (8) and FePzCl (9) were separately optimized in C4v
symmetry for each spin state. Similarly to previous results,30,52,53 it was found
that the porphyrin core size increased when going from the LS to the HS state,
while the Fe–Cl distance increased from the LS to the IS state, and then was
slightly decreased in the HS state (Tables S-IX and S-X of the Supplementary
material).
OPBE and S12g predicted the correct sextet spin ground state for both,
FePCl and FePzCl (see Table IV). In the case of FePCl, a sextet ground state was
predicted with the quartet higher in energy and vice versa for FePzCl, the quartet
state was lower in energy. In both cases, the LS state was considerably higher in
energy.
COSMO calculations revealed a clear and unambiguous solvent effect on the
electronic structure, Table IV. Introduction of the solvent favored the LS state,
and as such had small effects on the spin ground state of molecule 9 that has a
quartet ground state and a sextet quartet state that is similar in energy. In contrast,
for molecule 8, that is in an HS state experimentally and has a low-lying quartet
state, the quartet state is stabilized to the extent that it becomes the ground state
within all COSMO calculations. Of course, it should be added that the spin-state
splittings were investigated here through looking at the electronic energy and
SPIN STATE ENERGETICS OF IRON COMPLEXES 1407
hence, enthalpy and entropy effects were ignored. Both of these favor the high-
-spin states. Finally, S12g once again showed excellent agreement with the spin
state energetics obtained at the OPBE level of theory.
TABLE IV. Spin state energy differences (kcal mol-1, TZP basis) for FePCl (8) and FePzCl
(9), with OPBE and S12g functionals, in vacuum and COSMO
Geo.a SPb
FePCl FePzCl
Doublet Quartet Sextet Doublet Quartet Sextet
OPBE OPBE 18.4 3.9 0 12.5 0 3.7
OPBE cosmo 16.3 –1.0 0 15.6 0 7.6
S12g 15.7 1.5 0 12.8 0 4.9
S12g cosmo 13.8 –2.9 0 15.8 0 8.6
OPBE
cosmo
OPBE 18.0 4.8 0 11.6 0 2.9
OPBE cosmo 16.9 –1.7 0 16.6 0 8.2
S12g 15.0 2.3 0 11.8 0 4.2
S12g cosmo 14.1 –3.6 0 16.5 0 9.2
S12g OPBE 18.6 4.0 0 12.7 0 3.7
OPBE cosmo 16.3 –0.7 0 15.7 0 7.5
S12g 15.4 1.5 0 12.6 0 5.0
S12g cosmo 13.4 –2.8 0 15.4 0 8.6
S12g
cosmo
OPBE 18.3 4.5 0 12.0 0 3.2
OPBE cosmo 17.1 –1.6 0 16.8 0 8.1
S12g 15.0 2.0 0 11.8 0 4.6
S12g cosmo 14.0 –3.5 0 16.3 0 9.2
aGeometry optimization with frozen core electrons; bsubsequent single point calculations with all-electron basis sets
CONCLUSIONS
Within this paper, an extension of previous validation14 of DFAs for a
correct description of the spin states of Fe(II) and Fe(III) complexes is presented.
In the present contribution, structure relaxation of the LS, IS and HS states of the
iron compounds was allowed separately at the OPBE and S12g levels of theory
and thereby, a more stringent test on the reliability of functionals for providing
spin ground states of iron complexes was performed.
A detailed comparison with the already proven OPBE DFA for spin state
energetics, and experimental findings, revealed that S12g performed remarkably
well and thus, represents a very promising tool for studying spin states in com-
plicated transition metal systems. Moreover, for all iron complexes under inves-
tigation, S12g gave a good match with experimental geometries and thus, could
be considered as a good starting point for the investigation of transition metal
compounds.
SUPPLEMENTARY MATERIAL
Selected bond lengths, OPBE/TZP ligand binding energies, as well as coordinates of
optimized structures (as additional supplementary file), are available electronically from
http://www.shd.org.rs/JSCS/ or from the corresponding author on request.
1408 GRUDEN, STEPANOVIĆ and SWART
Acknowledgments. The following organizations are thanked for financial support: the
Ministerio de Ciencia e Innovación (MICINN, project CTQ2011-25086/BQU), the Ministerio
de Economia y Competitividad (MINECO, project CTQ2014-59212/BQU) and the DIUE of
the Generalitat de Catalunya (project 2014SGR1202, and Xarxa de Referència en Química
Teòrica i Computacional). Financial support was provided by MICINN and the FEDER fund
(European Fund for Regional Development) under grant UNGI10-4E-801, and the Serbian
Ministry of Education, Science and Technological Development (Grant No. 172035). This
work was performed within the framework of the COST action CM1305 ‘‘Explicit Control
Over Spin-states in Technology and Biochemistry (ECOSTBio)’’ (STSM reference: ECOST-
-STSM-CM1305-27360). We would like to thank Dr. A. W. Ehlers and Prof. K. Lammertsma
(VU Amsterdam, Netherlands) for help and fruitful discussions in the initial stages of this
study.
И З В О Д
РЕЛАКСАЦИЈА СПИНСКИХ СТАЊА КОД КОМПЛЕКСА ГВОЖЂА:
СЛУЧАЈ ЗА OPBE И S12g ФУНКЦИОНАЛЕ
МАЈА ГРУДЕН1, СТЕПАН СТЕПАНОВИЋ2 и MARCEL SWART3,4
1Хемијски факултет, Универзитет у Београду, Студентски трг 16, 11001 Београд, 2Центар за
хемију, ИХТМ, Универзитет у Београду, Његошева 12, 11001 Београд, 3Institut de Química
Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi,
Facultat de Ciències, 17071 Girona, Spain и 4Institució Catalana de Recerca i Estudis Avançats (ICREA),
Pg. Lluís Companys 23, 08010 Barcelona, Spain
Структуре девет комплекса гвожђа који показују разноврсност експериментално
одређених основних спинских стања оптимизоване су теоријом функционала густине
(DFT), а затим анализиране коришћењем различитих функционала. Извршена је обимна
валидациона студија новог S12g функционала, са дискусијом о утицају окружења, гео-
метрије, као и његових перформанси у односу на OPBE функционал који се већ показао
као добар. OPBE и S12g тачно предвиђају основно спинско стање код свих испитиваних
комплекса гвожђа. Како се S12g показао изузетно добро, он се може сматрати поузда-
ним за проучавање енергетике спинских стања у компликованим системима прелазних
метала.
(Примљено 11. јуна, ревидирано 14. јула, прихваћено 15. јула 2015)
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/ENU (Use these settings to create Adobe PDF documents best suited for high-quality prepress printing. Created PDF documents can be opened with Acrobat and Adobe Reader 5.0 and later.)
>>
/Namespace [
(Adobe)
(Common)
(1.0)
]
/OtherNamespaces [
<<
/AsReaderSpreads false
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(InDesign)
(4.0)
]
/OmitPlacedBitmaps false
/OmitPlacedEPS false
/OmitPlacedPDF false
/SimulateOverprint /Legacy
>>
<<
/AddBleedMarks false
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/AddRegMarks false
/ConvertColors /ConvertToCMYK
/DestinationProfileName ()
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/Downsample16BitImages true
/FlattenerPreset <<
/PresetSelector /MediumResolution
>>
/FormElements false
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]
/PDFXOutputIntentProfileSelector /DocumentCMYK
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/UseDocumentBleed false
>>
]
>> setdistillerparams
<<
/HWResolution [2400 2400]
/PageSize [612.000 792.000]
>> setpagedevice