Beruflich Dokumente
Kultur Dokumente
Konstantin L. Metlov
Donetsk Institute for Physics and Technology NAS, Donetsk, Ukraine 83114∗
(Dated: June 2, 2010)
A simple model for flexural phonons in graphite (and graphene, corresponding to the limiting
case of infinite distance between carbon planes) is proposed, in which the local dipolar moment is
assumed to be proportional to the curvature of the carbon sheets. Explicit expressions for dispersion
curves with full account for the long-range dipolar interaction forces are obtained and fitted to the
arXiv:0912.2559v4 [cond-mat.mes-hall] 1 Jun 2010
experimental data using a single adjustable parameter of the model. The parameter is expected to
depend on the ground state configuration of molecular π-orbitals, the same both for graphite and
for graphene. At decreasing carbon sheet separation (high pressures) the phonon spectrum displays
instability, corresponding to the graphite to diamond transition. Being explicitly based on the
local dipolar moments, the proposed simple model may prove useful for considering electron-phonon
interaction.
0011
11
0000
1111
4
00
11
00
11
11
00 000
111 00 111
000 11
0000
11
−1/2
00
11
carbon sheets is proposed with the emphasis on the long- 00
11
1 000
111
2 00
11
1 000
111
2 −1 11
00
11 00
00
11
00
11 000
111
00011
111 00
11
00
11 000
111
000
111 00
11 00
11
range interactions between the induced electric dipoles. 00 000
111 00
11
00
11 00
11
00
11
−1
00
11
1 000
111
2 00
11
−1 11
000
111 00
Due to orientation of the dipoles, the effect of such inter- 00
11
00
11 000
111
000
111 00
11
000
111
00
11
000
111
−1/2
actions on the flexural modes is the strongest. 000
111
The parameters of the model have clear physical mean-
ing and the interaction of the induced dipoles fully ac- FIG. 1: Sublattices in the graphite lattice. Inset shows
counts for their mutual orientation and distance. This schematically the electron charge density around a single sp2
is why the model can be expected to be transferable to hybridized carbon.
consideration of out-of-plane motion of atoms in many
(single-, many- and few-) layered carbon allotropes, dif-
fering only in the arrangement of atoms and, conse- charge with σ-electrons shown as −1 charged balls in
quently, of the dipoles. As a test, the flexural phonon the horizontal plane, and the π-electron shown as two
spectrum of graphite (and graphene, which is just a limit- −1/2 balls above and below the plane. The thicker line
ing case) is evaluated analytically and fitted to the exper- between the −1/2 balls symbolizes electric connection
imental data from the literature. Despite its simplicity, between these charges, arising from the fact that they
the model correctly demonstrates an expected instability represent the same single electron. The whole picture is
of graphite under pressure. the result of momentum quantization (fixing the shape
It is well known from Chemistry that carbon has va- of electronic clouds) and simple electrostatic repulsion.
lence of four and, in its layered form, makes three strong When three more carbon atoms are connected to the
chemical covalent bonds to neighbouring atoms (carbon original one, additionally to forming σ bonds, their π
or others), called the σ-bonds. The remaining electron clouds overlap, forming two “seas” of delocalized elec-
also participates in bonding, forming a weak π-bond, fa- trons above and below the plane, containing carbon nu-
mous for making the electron delocalized across the whole clei. π electrons spend half of their time above and half
molecule/crystal, which leads to many interesting prop- below the atom plane, and are free to move from one
erties of aromatic hydrocarbons, conduction of graphite atom to the other. Evoking σ-π separability and for-
and metallic-like conduction of graphene. The crucial im- getting about σ bonds we can imagine a single layer of
portance of π-bonds in hydrocarbons was realized even carbon as three layers of charge: a layer of +1 (per atom)
before the Hüskel model.5 These same bonds, as it will charges, representing the uncompensated charge of car-
be seen from the next, define mechanical properties of bon ions, and two -1/2 charged layers of π electrons on
layered carbon allotropes as well. both sides of it.
The electron density around a single sp2 -hybridised Having this picture in mind, imagine that such a tri-
carbon atom is sketched as a “ball and stick” model on layer carbon sheet is curved. Because both “seas” of elec-
the inset in Fig. 1 . Balls represent centers of negative trons are connected (it is the very same electrons after
2
all) the charge, pushed by the electrostatic repulsion, is The Hamiltonian is then
free to redistribute from the contracting to the expanding X m(au̇l )2
side. This creates a local electric dipolar moment (inter- m
~ l 2
H = + cpm
~)
acting with similar dipolar moments across the layer), in- 2
l,m
~
creases electrostatic energy of deformed electronic clouds !
and of the layer as a whole, producing the restoring force.
X X p l p l′ ′
m
~ m ~ 3(e~Z · ~δ)2
+ b 1− (,6)
To describe this process mathematically, consider a l,m
′ |~δ|3
~ l ,m
′ ~ |~δ|2 ~
δ=~l −~
ρm l
ρm
′
~ ~′
graphite-like lattice, split into four independent hexag-
onal Bravais sublattices 1-4, shown in Fig. 1. These where m is an atom’s mass, c and b are parameters of
sublattices are essentially the same, but only shifted the model (both have dimensions of energy). Express-
with respect to each other, so that position of a lat- ing this Hamiltonian in units of ma2 , we can introduce
tice site, identified by three-dimensional integer vector two characteristic frequencies ω0 =c/(ma2 ) and ω1 = βω0
~ = [i, j, k] ∈ Z 3 and number of the sublattice l, is
m with β = b/c. The parameter ω0 defines the overall en-
√ √ ergy scale (later we normalize it out), while β remains
l
~rm 3/2 − 3/2 0 i 0 the free parameter of the model.
~
= 3/2 3/2 0 · j + d~l + 0 um
l
~, Physically, the model attempts to capture essentials
a 0 0 2α k 1 of π-orbitals polarization during the deformation of each
| {z }
individual graphene sheet. Such deformation produces
~lm
ρ ~
local shift of the charge from one side of the sheet to an-
(1)
other, which can be represented as an additional charge
where a is the nearest neighbour distance in the lattice
density, superimposed over the original, undeformed, or-
planes, α is dimensionless inter-plane distance (in units of
l bital. The first potential energy term in (6) corresponds
a), um ~ is out-of-plane displacement of atoms (in units of to the electrostatic self-energy of this additional density,
a), the matrix (denoted in the further text as b) contains
while the second term models the interaction between
basis vectors of the lattice. The sublattice displacements
these redistributed charges across the whole lattice. This
(in units of a) are
reproduces precisely the extremely short-range (the self-
energy, taken simply as an independent parameter) and
0 0 0 0
d~1 = 0 , d~2 = 1 , d~3 = 1 , d~4 = 2 . long-range parts (by keeping the leading-order dipolar
0 0 α α terms) of the interaction between deformed orbitals while
(2) neglecting the higher-order multipole terms, whose con-
All neighbours of an atom at sublattice l belong to an- tribution peaks at intermediate distances.
other sublattice l̃ (by definition: 1̃ ≡ 2, 2̃ ≡ 1, 3̃ ≡ 4, To solve the model one may reexpress the Hamiltonian
l
4̃ ≡ 3). For the lattice (1) three nearest neighbours (6) in terms of the displacements um ~ and differentiate to
of an atom m ~ on sublattice l are the atoms m, ~ m ~+ find the force on an element m ~ of each of the four sub-
l =
− lattices. Representing the displacements by their Fourier
m
~ + ∆l [1, 0, 0], and m~l =m ~ + ∆l [0, 1, 0] of sublattice l̃,
components both in time and space
where ∆l = sign(l̃ − l); sign(x) is 1 if x ≥ 0, −1 if x < 0. Z
There can be several definitions of local surface cur- uml
(t) =
~ l )+ıωt 3~
ul (~k)e2πı(k·~ρm
~ d k, (7)
~
vature, but, for the case of small deformations of the
original lattice, all of them are essentially the same up
to a constant multiplier. It is convenient to measure the where ~k = [kX , kY , kZ ] and the explicit dependence on
curvature as a distance of the considered atom from the time t is shown, one gets the following usual secular equa-
plane, defined by its three nearest neighbours. The nor- tion for the frequency
mal to this plane at site m ~ of sublattice l is proportional 1~ 1~
u (k) A B C D u (k)
to 2 ~ ω02 B A E C u2 (~k)
2 u (k)
ω 3 ~ = · , (8)
l
~nm
~ = (~
rml̃
~ −~
rml̃
~+
l̃
) × (~rm~ −~
l̃
rm~−
), (3) u (k) 9 C E A B u3 (~k)
l l
u4 (~k) D C B A u4 (~k)
where cross denotes the vector product. The local dipolar
moment is then proportional to where the matrix (called the dynamical matrix and de-
noted here, including the numerical coefficient 1/9 in
l l l̃ l
l (~nm
~ · (~
rm~ −~ rm~ ))~
nm~ front, as M) is obviously self-adjoint. Its elements are
p~m
~ = l |2
, (4)
|~nm
~
A = 2a (2 + βS1 ) − 3β bS2 + bS2 (9)
where dot stands for the scalar product. Up to the first 2
B = β(b S2 + 9S2 ) − 6b (2 + βS1 ) (10)
order in atom displacements u we get p~ = [0, 0, p], where
p is C = β 3bU0 − 2aU3 + 3bU4 (11)
1 l̃ D = β b(bU0 − 6U3 ) + 9U4 (12)
l l l̃ l̃
pm
~ = u m
~ − u + u + u . (5) E = β (9U0 + b(bU4 − 6U3 )) , (13)
3 m ~ + −
m~l m~l
3
∗
Electronic address: metlov@fti.dn.ua http://fti.dn.ua/~ metlov/graphite_spectrum_v1.2.m.
1 8
K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, R. Nicklow, N. Wakabayashi, and H. G. Smith, Phys. Rev.
Y. Zhang, S. V. Dubonos, I. V. Grigorieva, and A. A. B 5, 4951 (1972).
9
Firsov, Science 306, 666 (2004). H. Yanagisawa, T. Tanaka, Y. Ishida, M. Matsue,
2
P. Avouris, Z. Chen, and V. Perebeinos, Nature Nanotech- E. Rokuta, S. Otani, and C. Oshima, Surf. Interface Anal.
nology 2, 605 (2007), ISSN 1748-3395. 37, 133 (2005).
3 10
V. Perebeinos and J. Tersoff, Phys. Rev. B 79, 241409 M. Mohr, J. Maultzsch, E. Dobardžić, S. Reich,
(2009). I. Milošević, M. Damnjanović, A. Bosak, M. Krisch, and
4
S. V. Kusminskiy, D. K. Campbell, and A. H. Castro Neto, C. Thomsen, Phys. Rev. B 76, 035439 (2007).
11
Phys. Rev. B 80, 035401 (pages 5) (2009). S. Siebentritt, R. Pues, K.-H. Rieder, and A. M. Shikin,
5
E. Hückel, Zeitschrift für Physik 70, 204 (1931). Phys. Rev. B 55, 7927 (1997).
6 12
R. Crandall (1998), preprint, URL N. Mounet and N. Marzari, Phys. Rev. B 71, 205214
http://people.reed.edu/~ crandall/papers/epstein.pdf. (2005).
7
K. L. Metlov, Mathematica program is available., URL