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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.

production1 and promising electronic properties,2 pro-

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duced demand for detailed study of all the related prop- 00

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erties of layered carbon. While conduction of graphene

is understood relatively well, there is still a need for a

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per such a model for out-of-plane (flexural) oscillations of

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carbon sheets is proposed with the emphasis on the long- 00

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2 −1 11

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range interactions between the induced electric dipoles. 00 000

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Due to orientation of the dipoles, the effect of such inter- 00

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−1/2

actions on the flexural modes is the strongest. 000

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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

100 the layers vanishes) and M splits into two 2 × 2 sub-

matrices. Expressions for A and B remain the same,

except that zeta function becomes 2-dimensional as the

80

EK ≅ 68 meV

matrix b in the expression for Sl loses its last row and

last column. The resulting spectrum is very similar to

energy, meV

ting of acoustic and optical branches. Please note that

40 even though the long-range interaction across the layers

is eliminated in graphene limit, the interaction inside the

20

layer still remains, giving the spectrum its specific shape.

Let us also note that in the present model displacement

of graphite layers as a whole, without flexing them, does

0

Γ M K Γ not generate any dipolar moment (4) and, thus, leaves

the energy invariant. According to the Goldstone the-

FIG. 2: Dispersion of flexural phonons in graphite across the orem, the presence of such continuos symmetry implies

first Brillouin zone, labels correspond to the well known high- the existence of an additional acoustic mode in the spec-

symmetry points. Experimental data are shown by circles,8 trum (the other acoustic mode is due to the energy in-

squares9 (as reproduced in Ref.12), triangles,10 diamonds.11 variance with respect to translation of the whole crystal).

Solid lines are calculated from (8)-(14) with β = 0.36, dashed In graphite this mode turns optic, acquiring a certain

lines are corrected by (15) with η = 0.036. amount of energy at Γ point due to macroscopic van der

Waals interaction between the carbon layers and depends

on their complete flexural phonon spectrum (8)-(14) as

with S√l = Zb(3, ~k, d~l ), Ul = Sl − 2 ~ ~

√ 3α Zb(5, k, dl ), a = well as temperature. This interaction can be simulated

2 cos 3πkX cos(3πkY ) + cos 2 3πkX + 6 and b = by introducing an additional phenomenological harmonic

√

1 + 2e−3iπkY cos 3πkX . This assumes the following coupling between neighbouring atoms on sublattices 2

definition of the Epstein zeta function and 3, resulting in the following addition to the dynamic

matrix in (8)

~ =

X

′ e2πı~c·A·~n

ZA (s, ~c, d) s , (14)

A · ~n − d~

0 0 0 0

n∈Z D

~

0 2 −1 − e4πıkZ 0

D′ = η

0 −1 − e −4πık

, (15)

where prime near the sum means that singular terms are Z

2 0

excluded, A is an arbitrary D×D matrix, s is (in general) 0 0 0 0

complex scalar and ~c, d~ are arbitrary D-vectors. The

vectors d~l are from (2) with d~0 = [0, 0, α]. where η is a parameter. The effect of this addition is

Epstein zeta function can be very efficiently evaluated6 mostly localized in the neighbourhood of Γ point (see

by a computer program.7 The four branches of flexural dashed line in Fig. 2, corresponding to the best-fit value

phonon spectrum of graphite at any point in ~k-space are of η = 0.036). In principle, the value of η can be calcu-

then just the square roots of eigenvalues of the matrix M, lated on the basis of the present model (by also including

defined by (8)-(14). Apart from the parameter ω0 , defin- the repulsion between the layers due to exchange interac-

ing the overall frequency scale, these branches depend on tion), but, while its introduction results in a better fit to

graphite interlayer separation α = 2.34, taken from the the data, it is methodologically wrong to try to model the

experiment, and the free parameter of the model β. macroscopic interaction inside the microscopic Hamilto-

A wealth of experimental data on phonon spectrum of nian (6).

graphite is available in the literature.8–11 Some of these One may try to add σ-bonds stretching to the model

data are shown in Fig. 2 along with dispersion curves by introducing the following term into the Hamiltonian

predicted by the considered model for β = 0.36, giving (6):

the best fit to the data. The value of ω0 = 51meV was γ X l̃

l 2 l 2 l 2

obtained by fixing the values of the spectrum at K point. Hσ = |~rm

~l+ −~

rm~ | + |~

rm

l̃

~l− − ~

rm~ | + |~

rm

l̃

~l − ~

rm~ | ,

There is a slight disagreement near M , which can be at- 2

l,m

~

tributed either to the oversimplification of the model, ne- (16)

glecting the higher-order multipole terms, or may be even where γ is a free parameter. This models σ-bonds as

to the experimental errors, which, at least for one set of harmonic strings with an equilibrium length of 1, produc-

measurements,8 increase on approach to M . Provided ing, up to the first order in displacements, an additional

l

there is a single adjustable parameter, the agreement be- force −6γpm ~ at each site (proportionality of this force

tween the model (solid line) and the experiment is very to the magnitude of the local dipolar moment is just a

good. convenient coincidence). The corresponding dynamical

The spectrum of graphene can be obtained as a limit matrix can be obtained by adding 3γ to A in Eq. (9)

4

√

and −γ(1 + e3ıπkY cos 3πkX ) to B in Eq. (10). How- with respect to the widely used for this task Born-von

ever, fitting the resulting spectrum to the experimental Kármán type models, necessitating to include several

data, produces (up to the fitting error) γ = 0. It means, nearest neighbours (and, consequently, many parame-

there is no contribution of σ-bonds stretching to flexural ters) into consideration to obtain comparable agreement

phonon spectrum, which may be a consqeuence of their to the experiment. Because the interactions in the pre-

strong anisotropy. There is no need to introduce an ad- sented model are purely electrostatic, their dependence

ditional parameter γ to obtain the fit, shown in Fig. 2. on inter-atomic and inter-layer distance is explicit. The

The interlayer interaction becomes progressively model is not specific to graphene or graphite. The ex-

stronger if one presses the graphite, reducing the inter- pression for stress-induced dipolar moment and a similar

layer distance α. In this case splitting of the acoustic Hamiltonian may be useful while considering other lay-

and optical branches rapidly grows, until, at a critical ered carbon allotropes, such as single- and multi- walled

value of α = 0.91, one of the acoustic branches touches nano-tubes, fullerenes etc.

the horizontal axis at point K. At smaller α the cor-

responding eigenvalue of M becomes negative, meaning The effect of higher order multipoles or other quickly

that the lattice is unstable. This happens at interlayer decaying short-range interactions would correspond to a

distance approaching the intra-layer distance between certain simple addition to the dynamical matrix, simi-

carbon atoms, suggesing that it corresponds to lability lar to discussed above. Since the most important (and

boundary of graphite → diamond transition. more difficult to evaluate) long-range contribution is al-

To conclude, the presented simple model, by explicitly ready taken into account (and produces a very complete-

including the long-range dipolar interactions, quantita- looking spectrum), one can expect the other contribu-

tively reproduces flexural phonon spectrum of graphite tions to be small and local. Thus, it can be hoped that

and graphene using a single, universal for all layered the model can be a solid basis for further quantitative

carbon allotropes, parameter β. This is an advantage improvement.

∗

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

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