Electronic structure and magnetic properties of graphite intercalated with 3d-metals
Electronic structure and magnetic properties of graphite-based systems with intercalated 3d-transition metal atoms (V, Cr, Mn, Fe, Co, Ni) were calculated ab initio using the density functional theory. The presence of different magnetic states depending on the type of inserted M atoms is revealed f...
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| Cite this: | Electronic structure and magnetic properties of graphite intercalated with 3d-metals / G.E. Grechnev, A.A. Lyogenkaya, Yu.A. Kolesnichenko, Yu.I. Prylutskyy, R. Hayn // Физика низких температур. — 2014. — Т. 40, № 5. — С. 580-584. — Бібліогр.: 17 назв. — англ. |
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Grechnev, G.E. Lyogenkaya, A.A. Kolesnichenko, Yu.A. Prylutskyy, Yu.I. R., Hayn 2017-06-07T05:40:59Z 2017-06-07T05:40:59Z 2014 Electronic structure and magnetic properties of graphite intercalated with 3d-metals / G.E. Grechnev, A.A. Lyogenkaya, Yu.A. Kolesnichenko, Yu.I. Prylutskyy, R. Hayn // Физика низких температур. — 2014. — Т. 40, № 5. — С. 580-584. — Бібліогр.: 17 назв. — англ. 0132-6414 PACS 71.20.Tx, 75.10.Lp, 75.30.Cr, 81.05.U https://nasplib.isofts.kiev.ua/handle/123456789/119495 Electronic structure and magnetic properties of graphite-based systems with intercalated 3d-transition metal atoms (V, Cr, Mn, Fe, Co, Ni) were calculated ab initio using the density functional theory. The presence of different magnetic states depending on the type of inserted M atoms is revealed for hexagonal P6/mmm and P6 3/mmc crystall structures. The values of magnetic moments appeared to be governed by the p–d hybridization, and by variations of exchange interactions with intercalation. The results of calculations clearly indicate itinerancy of the 3d-electrons of inserted M atoms. This work was performed using computational facilities of grid-cluster ILTPE — B. Verkin Institute for Low Temperature Physics and Engineering of the National Academy of Sciences of Ukraine. en Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України Физика низких температур Низкотемпеpатуpный магнетизм Electronic structure and magnetic properties of graphite intercalated with 3d-metals Article published earlier |
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Electronic structure and magnetic properties of graphite intercalated with 3d-metals |
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Electronic structure and magnetic properties of graphite intercalated with 3d-metals Grechnev, G.E. Lyogenkaya, A.A. Kolesnichenko, Yu.A. Prylutskyy, Yu.I. R., Hayn Низкотемпеpатуpный магнетизм |
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Electronic structure and magnetic properties of graphite intercalated with 3d-metals |
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Electronic structure and magnetic properties of graphite intercalated with 3d-metals |
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Electronic structure and magnetic properties of graphite intercalated with 3d-metals |
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Electronic structure and magnetic properties of graphite intercalated with 3d-metals |
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electronic structure and magnetic properties of graphite intercalated with 3d-metals |
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Grechnev, G.E. Lyogenkaya, A.A. Kolesnichenko, Yu.A. Prylutskyy, Yu.I. R., Hayn |
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Grechnev, G.E. Lyogenkaya, A.A. Kolesnichenko, Yu.A. Prylutskyy, Yu.I. R., Hayn |
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Низкотемпеpатуpный магнетизм |
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Низкотемпеpатуpный магнетизм |
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2014 |
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English |
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Физика низких температур |
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Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України |
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Article |
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Electronic structure and magnetic properties of graphite-based systems with intercalated 3d-transition metal
atoms (V, Cr, Mn, Fe, Co, Ni) were calculated ab initio using the density functional theory. The presence of different magnetic states depending on the type of inserted M atoms is revealed for hexagonal P6/mmm and
P6
3/mmc crystall structures. The values of magnetic moments appeared to be governed by the p–d hybridization,
and by variations of exchange interactions with intercalation. The results of calculations clearly indicate itinerancy of the 3d-electrons of inserted M atoms.
|
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0132-6414 |
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https://nasplib.isofts.kiev.ua/handle/123456789/119495 |
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Electronic structure and magnetic properties of graphite intercalated with 3d-metals / G.E. Grechnev, A.A. Lyogenkaya, Yu.A. Kolesnichenko, Yu.I. Prylutskyy, R. Hayn // Физика низких температур. — 2014. — Т. 40, № 5. — С. 580-584. — Бібліогр.: 17 назв. — англ. |
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AT grechnevge electronicstructureandmagneticpropertiesofgraphiteintercalatedwith3dmetals AT lyogenkayaaa electronicstructureandmagneticpropertiesofgraphiteintercalatedwith3dmetals AT kolesnichenkoyua electronicstructureandmagneticpropertiesofgraphiteintercalatedwith3dmetals AT prylutskyyyui electronicstructureandmagneticpropertiesofgraphiteintercalatedwith3dmetals AT rhayn electronicstructureandmagneticpropertiesofgraphiteintercalatedwith3dmetals |
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2025-11-25T12:22:15Z |
| last_indexed |
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Low Temperature Physics/Fizika Nizkikh Temperatur, 2014, v. 40, No. 5, pp. 580–584
Electronic structure and magnetic properties of graphite
intercalated with 3d-metals
G.E. Grechnev, A.A. Lyogenkaya, and Yu.A. Kolesnichenko
B. Verkin Institute for Low Temperature Physics and Engineering of the National Academy of Sciences of Ukraine
47 Lenin Ave., Kharkov 61103, Ukraine
E-mail: grechnev@ilt.kharkov.ua
Yu.I. Prylutskyy
Taras Shevchenko National University of Kyiv, Kyiv, 01601 Ukraine
Roland Hayn
Universite d’Aix-Marseille, IM2NP, 13397 Marseille Cedex 20, France
Received December 23, 2013
Electronic structure and magnetic properties of graphite-based systems with intercalated 3d-transition metal
atoms (V, Cr, Mn, Fe, Co, Ni) were calculated ab initio using the density functional theory. The presence of dif-
ferent magnetic states depending on the type of inserted M atoms is revealed for hexagonal P6/mmm and
P63/mmc crystall structures. The values of magnetic moments appeared to be governed by the p–d hybridization,
and by variations of exchange interactions with intercalation. The results of calculations clearly indicate itineran-
cy of the 3d-electrons of inserted M atoms.
PACS: 71.20.Tx Fullerenes and related materials; intercalation compounds;
75.10.Lp Band and itinerant models;
75.30.Cr Saturation moments and magnetic suscepti;
81.05.U– Carbon/carbon-based materials.
Keywords: intercalated graphite, electronic structure, magnetic moments, MC6.
1. Introduction
Graphite is well known and investigated for decades ma-
terial due to its quasi-two-dimensional structure, which
gives rise to highly anisotropic electronic properties and
provides an exciting avenue for testing physical concepts in
lower dimensions [1–3]. Graphene, a single layer of graphite
with two-dimensional structure and unique physical proper-
ties, recently emerged as one of the most promising low-
dimensional nanomaterials [4,5]. Basically, both these mate-
rials are nonmagnetic ones, however a moderate magnetism
can be induced by ion implantation and point defects [5,6].
On the other hand, due to the layered hexagonal crystal
structure of graphite, there is also a possibility to induce
ferromagnetism by intercalation of magnetic 3d-metal ions
into the van der Waals gap between carbon layers [7,8].
The carbon atoms within the basal plane are bound to-
gether by strong covalent σ-bonds, while atoms in adjacent
layers are weakly bound by van der Waals bonds [8,9].
As a result it is easy to intercalate graphite with alkali met-
als, and this intercalation changes both the crystal and elec-
tronic structures [1,2]. The intercalation of atoms M into
graphite can transform the stacking sequence of hexagonal
planes from ABAB... to aligned graphene planes with M
atoms inserted into a α superlattice — AαAαAα. Whereas
the intercalation increases noticeably the interlayer separa-
tion (by 10% in LiC6), the intralayer lattice constant a is
only slightly dilated [2].
Researches of magnetic and transport properties of car-
bon compounds with magnetic 3d-metals have high poten-
tial in a context of spintronics and its practical applications.
The different valences of the 3d-atoms result in a range of
induced magnetic moments and peculiar spatial spin density
distribution, what is needed for spintronic applications. It is
anticipated, that selective induction of spin-polarization can
be utilized in spintronic and nanoelectronic devices.
© G.E. Grechnev, A.A. Lyogenkaya, Yu.A. Kolesnichenko, Yu.I. Prylutskyy, and Roland Hayn, 2014
mailto:grechnev@ilt.kharkov.ua
Electronic structure and magnetic properties of graphite intercalated with 3d-metals
The basic aim of the present work is to study how the in-
tercalation of different 3d-metal ions (M = Cr, Mn, Fe, Co)
affects the electronic structure and magnetic properties of
graphite. Obviously, the hybridization between the p-states
of carbon and 3d-states of a guest metal is expected, and
the methods of the density functional theory (DFT) can be
applied. The specific tasks of this study are to investigate
theoretically magnetic characteristics of the intercalated
graphite-based systems and to reveal electronic structure
features which can promote magnetic ordering in these
systems, and also transition to the half-metal state.
2. Electronic structure and magnetism
In order to analyze the magnetic properties of graphite
intercalated with 3d-metals, the ab initio calculations of the
electronic structure and magnetic moments of MC6 com-
pounds were carried out within DFT. We have taken into
consideration hexagonal crystal structures, corresponding
to the space groups P6/mmm and P63/mmc [10]. The struc-
tural parameters of MC6 were chosen according to data of
Refs. 8,10.
Ab initio calculations of the electronic structure of MC6
were performed by employing a full-potential all-electron
linear muffin-tin orbital method (FP-LMTO, code RSPt
[11,12]). This full-potential method was successfully ap-
plied for complex systems with open [13] and layered [9]
structures having substantially inhomogeneous charge den-
sities. The exchange-correlation potential was treated with-
in both the local spin density approximation (LSDA, [14])
and the generalized gradient approximation (GGA, [15]) of
the DFT. In our calculations the spin-orbit coupling was
taken into account, though its effect appeared to be very
small comparatively with scalar relativistic effects.
In this work the valence electronic charge densities of
MC6 were calculated, and the corresponding results for
FeC6 are shown in Fig. 1. The evaluated electronic charge
densities of other MC6 compounds appeared to be similar.
The distribution of charge density in the carbon basal plane
clearly indicates the covalent character of corresponding
σ-bonds. On the other hand, the charge density of Fe atom is
more localized, and the chemical bond of Fe with atoms of
carbon has presumably ionic character, due to the notable
charge transfer.
In addition, to investigate the chemical bonding in
MC6, the balanced crystal orbital overlap populations
BCOOP [16] was calculated within the FP-LMTO tech-
nique. The BCOOP is defined as the orbital population
weighted density of states with a “balancing” denominator
[17], and this method is similar to the well known COOP,
which is the solid-state generalization of the quantum
chemical quantity called crystal orbital overlap population.
A knowledge of the M–C bonding is important to under-
stand the role of implanted 3d-magnetic atoms for different
types of magnetic ordering [7]. In our case it was found
that hybridization of p-states of carbon and d-states of tran-
sition metal M is small, and this provides partially ionic–
partially metallic character of M–C bonds (see Fig. 2).
The calculated within LSDA magnetic moments of MC6
are in both P6/mmm and P63/mmc structures the induced
spin polarization appears for V, Cr, Mn, Fe, and Co interca-
lation, providing magnetic moments listed in Table 1 (per
corresponding MC6 formula unit). The intercalation of
graphite with Ni does not result in a magnetic state for both
structures. For all intercalated atoms M the induced magnet-
ic moment differs in P6/mmm and P63/mmc structures, due
to different average M–C bonding. The smaller correspond-
ing bonding lengths, the larger is the magnetization.
When the total magnetic moment decreases along the
series Mn–Fe–Co, the corresponding localized moments in
MT-sphere are obviously reduced in magnitude. At the
same time, a weak spin density develops in the interstitial
region between the atomic sites. In the case of NiC6 the
filling of all 3d-orbitals and hybridization of the 3d-orbitals
with p-orbitals of carbon, results in zero magnetic moment.
Fig. 1. Contour plots of total valence-electron charge density of FeC6 in P63/mmc structure: in the vertical (010) plane (a), and in the
basal (001) plane (b).
Low Temperature Physics/Fizika Nizkikh Temperatur, 2014, v. 40, No. 5 581
G.E. Grechnev, A.A. Lyogenkaya, Yu.A. Kolesnichenko, Yu.I. Prylutskyy, and Roland Hayn
As can be seen from the calculated densities of electronic
states (DOS) ( )N E in Figs. 3, 4, 5, 6, and 7, M intercalated
graphite basically develops a metallic state. The spin-
polarized ( )N E revealed that the presence of 3d-atoms sub-
stantially enhances DOS at the Fermi level EF, compara-
tively with the semimetallic pure graphite [9].
Analysis of the calculated ( )N E indicates that for Mn,
Fe, and Co intercalation the spin-majority d-states are situ-
ated predominantly below the Fermi level, whereas the
main contribution to ( )FN E comes from the spin-mino-
rity d-states of the 3d-metal atom (see Figs. 5, 6, and 7).
It should be noted that in MnC6, FeC6, and CoC6 there is
very small contribution of the spin-majority states to
( ).FN E The corresponding “pseudo-gap” in ( )N E for the
spin-majority states provides a possibility of formation of
spin half-metal state.
On the other hand, in VC6 and CrC6 there are substantial
and competing contributions to ( )FN E from both spin-
majority and spin-minority d-states (see Figs. 3 and 4),
which make impossible realization of half-metal state. The
dominating p-orbitals of carbon are strongly hybridized
with d-states in all studied MC6 compounds, however the
differences between spin-majority and spin-minority DOS
of carbon are small, as well the corresponding contribu-
tions to magnetic moments of MC6. In case of Ni intercala-
tion, the almost filled 3d-orbitals virtually do not provide
spin-polarized DOS at the Fermi level, and this explains
the nonmagnetic behavior of NiC6.
Fig. 2. Calculated BCOOP of FeC6 in P63/mmc structure.
Table 1. Magnetic moments of MC6 (per formula unit)
Structure M Magnetic moment (µB)
V 0.88
Cr 1.59
P6/mmm Mn 2.89
Fe 1.99
Co 0.99
V 1.42
Cr 2.53
P63/mmc Mn 2.66
Fe 1.78
Co 0.24
Fig. 3. Calculated spin-majority (V is solid line, C is dashed-
dotted line) and spin-minority (V is dashed line, C is dotted line)
partial DOS for the configuration P6/mmm of VC6. The position
of Fermi level at 0 eV is marked by a vertical line.
Fig. 4. Calculated spin-majority (Cr is solid line, C is dashed-
dotted line) and spin-minority (Cr is dashed line, C is dotted line)
partial DOS for the configuration P6/mmm of CrC6. The position
of Fermi level at 0 eV is marked by a vertical line.
582 Low Temperature Physics/Fizika Nizkikh Temperatur, 2014, v. 40, No. 5
Electronic structure and magnetic properties of graphite intercalated with 3d-metals
3. Conclusion
In order to investigate a possibility to obtain the half-
metal state in carbon-based materials, we have studied the
spin-polarized electronic structure of graphitic network
intercalated with 3d-transition metal atoms V, Cr, Mn, Fe,
Co, and Ni. The electronic structure of these graphitic sys-
tems is modified after intercalation due to hybridization
of the carbon p-orbitals with the d-orbitals of a transition
metal. It appears that V, Cr, Mn, Fe, and Co induce spin-
polarization in hexagonal configurations, whereas Ni pro-
vides a metallic system with zero magnetic moment. As a
result, the hybridization and spin polarization due to inter-
calated magnetic 3d-transition metal atoms appears to be
favorable for realization of graphite-based ferromagnetic
half-metal state in MnC6, FeC6 and CoC6 systems.
This work was performed using computational facilities
of grid-cluster ILTPE — B. Verkin Institute for Low Tem-
perature Physics and Engineering of the National Academy
of Sciences of Ukraine.
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dotted line) and spin-minority (Co is dashed line, C is dotted line)
partial DOS for the configuration P6/mmm of CoC6. The position
of Fermi level at 0 eV is marked by a vertical line.
Low Temperature Physics/Fizika Nizkikh Temperatur, 2014, v. 40, No. 5 583
G.E. Grechnev, A.A. Lyogenkaya, Yu.A. Kolesnichenko, Yu.I. Prylutskyy, and Roland Hayn
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584 Low Temperature Physics/Fizika Nizkikh Temperatur, 2014, v. 40, No. 5
1. Introduction
2. Electronic structure and magnetism
3. Conclusion
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