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Chapter 1
Lattice Dynamics
When the structure and cohesion of solids are studied, we assume that the
atoms or ions in solids stay at their respective equilibrium positions. This
is sufficient for the purpose of studying their structural and binding properties. However, when we pursue to understand many other properties of
solids, such as their thermodynamic properties, the picture of static atoms
or ions in solids becomes inadequate and their dynamics must be taken into
consideration. As a matter of fact, atoms or ions in solids never stay persistently at their equilibrium positions at finite temperatures. Instead, they
move back and forth (that is, they vibrate or oscillate) constantly about
their equilibrium positions. This kind of motion is referred to as lattice vibrations and the entire subject related to lattice vibrations is called lattice
dynamics or crystal dynamics.
Lattice dynamics can be said to be the oldest branch of solid state
physics. To be convincing, we now trace some of the early important developments in lattice dynamics. In 1907, Einstein1 published his work on
the lattice specific heat, entitled Plancks theory of radiation and the theory of specific heat (the birth of the Einstein model on the lattice specific
heat). In 1912, Born and von Karman2 published their work on lattice
vibrations, entitled On vibrations in space lattices (the birth of the formal
theory of lattice dynamics), and Debye3 published his work on the lattice
specific heat, entitled On the theory of specific heat (the birth of the Debye
model on the lattice specific heat). There are many other early landmark
developments.
1 A.
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4 B.
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Lattice Dynamics
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(1.1)
iI
where m is the mass of an electron, MI and ZI e are the mass and charge
of nucleus I, ri and RI denote the positions of the ith electron and the Ith
e is the Hamiltonian of the subsystem of electrons,
nucleus, respectively, H
n is the Hamiltonian of the subsystem of nuclei, and H
en is the interaction
H
Hamiltonian between electrons and nuclei.
The Hamiltonian in Eq. (1.1) is referred to as the fundamental Hamiltonian of a solid in the sense that all the properties of the solid can be
could be found exactly.
computed if the eigenvalues and eigenstates of H
Unfortunately, it is not in sight at all that any one could accomplish that.
Therefore, we have no choice but make some approximations to be able
to proceed to understand any physical properties of a solid. Because
the electrons and ions are coupled together, the separation of the electronic and nuclear motions would be of great help. This is provided by
the BornOppenheimer approximation that is also known as the adiabatic
approximation.
This chapter is organized as follows. The BornOppenheimer approximation is first introduced in Sec. 1.1 so that we can concentrate only on the
motion of nuclei (or atoms or ions) thereafter. We then attempt to develop
the classical theory of lattice vibrations as gently as possible, with the full
classical theory established in the end.
In Sec. 1.2, we introduce the harmonic approximation and derive the
harmonic lattice potential energy for a three-dimensional crystal with a
multi-atom basis. We then proceed to find the normal modes of lattice
vibrations of a solid under the harmonic approximation. Attention should
be paid to the way we solve the classical equations of motion of atoms: We
expand the displacement of an atom in terms of its Fourier components (i.e.,
make a Fourier transformation of the displacement of atoms with respect
to positions of primitive cells and time) so that the differential equations
are converted into algebraic equations.
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BornOppenheimer Approximation
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Lattice Dynamics
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(1.2)
can be solved with the nuclei remaining in the configuration R, where E(R)
is the electronic eigenenergy in the nuclear configuration R. Inserting the
above equation into Eq. (1.3), we obtain
n (R) + E(R) (r; R)(R) = E(r; R)(R).
H
(1.5)
The motion of the nuclei is thus separated from that of the electrons. This
is a great step forward since we now have a recipe to solve the eigenequation
of the Hamiltonian of the solid albeit it is done approximately. If the variables in Eq. (1.3) had been separated exactly, we would have had an exact
solution to the problem. In a sense, the BornOppenheimer approximation
is equivalent to solving Eq. (1.2) with the separation of variables. Hence,
the impreciseness in the BornOppenheimer approximation is caused by
the forceful application of the separation of variables to Eq. (1.2).
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(1.7)
I6=J
2MI
I
R
R
with dr = dr1 dr2 drNe . Due to the afore-mentioned slow motion
of the nuclei in comparison with the electrons, the non-adiabatic contribution is usually small and can be taken into account perturbatively. The
non-adiabatic contribution is very important to some physical properties
of a solid since it describes the interaction between electrons and lattice
vibrations.
When only the electronic states are of concern, Eq. (1.4) can be solved
for a set of fixed nuclear positions (i.e., a fixed nuclear configuration). In
consideration of the large masses and slow motion of the nuclei, their motion is often solved using classical mechanics. In such a case, a potential
energy surface can be mapped out by solving Eq. (1.4) for different nuclear
configurations and then used in classical computations for the motion of
nuclei.
In practice, the nuclei in Eq. (1.2) are often replaced with ions or ion
cores since the core electrons play a much less role than valence electrons
in determining the properties of a solid.
1.2
From the above discussions, we see that the nuclear potential energy, referred to as the lattice potential energy hereafter, can be obtained only
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Lattice Dynamics
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after the electronic motion has been solved for all the nuclear configurations. Thus, it seems that the understanding of the lattice dynamics of a
crystal is impossible without the knowledge of the electronic states. However, the lattice potential energy can also be obtained empirically with the
input from experiments. Such an approach is called the pseudopotential
method. In any event, the lattice potential energy is assumed to be known
from now on. In this sense, our treatment is of phenomenological nature.
With the kinetic energy expressed in terms of momenta of atoms, the lattice
Hamiltonian is given by
X p2
i
=
H
+ (r1 , r2 , , rN ),
(1.9)
2m
i
i
where we have used the lowercase letter i to label an atom, the lowercase
letter m to denote its mass, the bold lowercase letter p to denote its momentum, and the bold lowercase letter r to denote its position. The bold
capital letter R is now reserved for the lattice vectors. Also, for brevity we
will generally refer to atoms as the constituents of a crystal in this section
even though they may be ions. But, ions will be used when an ionic crystal is explicitly referred to. For pairwise interactions between atoms, the
lattice potential (r1 , r2 , , rN ) can be written as
(r1 , r2 , , rN ) =
N
1 X
(ri rj ),
2
(1.10)
i6=j=1
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the anharmonic terms become important. For such crystals, the effects of
the cubic and quartic anharmonic terms are often considered.
We now consider a three-dimensional crystal with a multi-atom basis.
To be able to keep track of the algebras comfortably, we first describe clearly
how the atoms are labeled and their positions denoted.
As generally done, we label each primitive cell by the lattice site on
which the primitive cell sits. Thus, the ith primitive cell locates on the
ith lattice site and its position vector is given by Ri that is the lattice
vector of the ith lattice site. Because of the presence of bases of atoms in
a crystal, the number of atoms in each primitive cell is greater than one.
The atoms within each primitive cell are indexed by positive integers, with
Greek letters (, , ) often used for the variables of indices. For a p-atom
basis, we have = 1, 2, , p. To refer to an atom within a primitive cell,
we can say the th atom within the ith primitive cell. The position of
an atom within a primitive cell is given in the local Cartesian coordinate
system associated with the primitive cell with the origin at the tip of the
position vector of the primitive cell, denoted by d for the th atom. Thus,
the equilibrium position of the th atom within the ith primitive cell in a
crystal is given by Ri + d .
Shown in Fig. 1.1 is a simple cubic crystal with a two-atom basis. The
CsCl crystal has such a structure. Because atom 1 in a primitive cell locates
at the tip of the position vector of the primitive cell, its position vector is
zero in the local Cartesian coordinate system associated with the primitive
cell and is thus not shown in the figure.
With the displacement of an atom from its equilibrium position taken
into account, the instantaneous position ri of the th atom within the ith
primitive cell is given by
ri = Ri + d + ui .
(1.11)
(1.12)
1 X
(Ri + d Rj d + ui uj )
2
(1.13)
i6=j
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Lattice Dynamics
d2 ui2
ui1
i
ri1
y
ri2
Ri
O
x
x
(a)
(b)
(c)
Fig. 1.1 Lattice vibrations in a simple cubic crystal with a multi-atom basis. (a) Static
lattice. To indicate that the atoms of the second kind locate at the centers of the cubes
(the primitive cells), the body diagonals of one cube are drawn. (b) Dynamic lattice.
The ith primitive cell is shaded and marked by i close to its rear lower-left corner that
is chosen as the origin of the local Cartesian coordinate system associated with the
primitive cell. The global Cartesian coordinate system is also shown. (c) Description of
atomic positions. Shown are the position Ri of the ith primitive cell, the position d2
of the second atom within the primitive cell, the displacements ui1 and ui2 , and the
instantaneous positions ri1 and ri2 of the two atoms within the primitive cell. Note
that the position vector d1 of the first atom is zero within the local Cartesian coordinate
system associated with the primitive cell and is not shown.
1X
(ui, uj, ) (Ri +d Rj d )(ui, uj, ), (1.14)
+
2
(1.15)
(1.16)
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10
where
0 =
1 X
(Ri + d Rj d )
2
(1.17)
i6=j
is the total cohesive (or lattice) energy. The first-order term vanishes because of the equilibrium condition
X
(Ri + d Rj d ) = 0.
i (i6=j)
1X X
= 0 +
(Ri +d Rj d )(ui, ui, ui, uj, )
2 ij
,
X
1X X
= 0 +
(Ri + d Rj 0 d 0 ) ij
2 ij
,
j0 0
(Ri + d Rj d ) ui, uj,
= 0 +
1X X
ui, D, (Ri Rj )uj, ,
2 ij
(1.18)
(Ri + d Rj d ).
(1.19)
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11
Lattice Dynamics
1.3
Fi, =
i j ,
1X X
=
D0 , 0 (Ri0 Rj )uj, ii0 0 0
2 0 0 0
i j ,
+ ui0 0 , 0 D0 , 0 (Ri0 Rj )ij
X
D, (Ri Rj )uj, .
=
j
(1.21)
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12
(1.22)
where m is the mass of the th atom in a primitive cell. Note that there
is an equation of the above form for each atom in the crystal and for each
coordinate component of the displacement of each atom. Thus, we have
3N p equations in three dimensions. The solutions to the above equations
are to be found by expressing ui, in terms of its Fourier components
X
1
ui, (t) =
Q (k, )ei(kRi t)
(1.23)
N
m
k
with N the total number of primitive cells in the crystal. The fact that
ui, (t) takes only on real values leads to the property that Q (k, ) =
Q (k, ) for the Fourier coefficient Q (k, ) .
1.3.2
The allowed values of k are to be found from the Born-von Karman boundary condition that, for a crystal with a multi-atom basis, is stated as follows
ui1 +N1 , i2 i3 , , (t) = ui1 , i2 +N2 , i3 , , (t) = ui1 i2 , i3 +N3 , , (t)
= ui1 i2 i3 , , (t),
(1.24)
(1.25)
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Lattice Dynamics
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13
(1.26)
We now find the allowed values of frequency . Substituting Eq. (1.23) into
Eq. (1.22) yields
Q (k, ) X i(kRi t)
m 2
e
N
k
XX
Q (k, ) i(kRj t)
=
D, (Ri Rj )
e
,
N m
k j
X
X
1
2 Q (k, ) =
D, (Ri Rj )eik(Ri Rj ) Q (k, ),
m m j
X
D, (k) 2 Q (k, ) = 0,
(1.27)
(1.28)
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14
D, (Ri Rj ), we have
D,
(k) =
X
1
D, (Ri Rj )eik(Ri Rj )
m m j
X
1
D, (Rj Ri )eik(Ri Rj )
m m j
X
1
=
D, (Ri Rj )eik(Ri Rj ) ,
m m j
(1.29)
that is,
D,
(k) = D, (k) or D (k) = D(k).
(1.30)
To arrive at the final result on the third line in Eq. (1.29), we have set
Rj Ri Ri Rj .
We now go back to the equations in Eq. (1.27). First of all, they imply
that the squares of the frequencies of the normal modes are the eigenvalues
of the dynamical matrix. The Hermitian property of the dynamical matrix
guarantees that all the solutions of 2 are real. They are also nonnegative
for stable crystals. Since these equations are homogeneous linear equations
for Q (k, )s, the secular equation for the determination of frequencies
follows from the sufficient and necessary condition for the existence of nontrivial solutions
det |D, (k) 2 | = 0.
(1.31)
3p
X
s=1
Q (k, ks )ks + Q (k, ks ),ks .
(1.32)
We now find out how many branches among the 3p branches are acoustical branches and how many are optical branches. For this purpose, we
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Lattice Dynamics
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15
(1.34)
Noticing that the above equation is just the eigenequation for D(0), we
see that the zero eigenvalues of D(0) correspond to acoustical branches.
Therefore, the number of acoustical branches is given by the dimension
of D(0) less its rank. The rank of D(0) can be found by the Gaussian
elimination method in linear algebra. With the rows and columns of D(0)
indexed in the order = 1x, 1y, 1z, 2x, 2y, 2z, , px, py, pz, matrix
D(0) takes on the following form
D11, xx X D11, xy X D11, xz
m1
m1
m1
j
j
j
X
D21, xx X D21, xy X D21, xz
m2 m1 j
m2 m1 j
m2 m1
j
..
..
..
.
.
.
mp m1 j
mp m1 j
mp m1
j
X
m1 mp j
m1 mp j
m1 mp
j
X D2p, xx X D2p, xy X D2p, xz
m
m
m
m
m
m
p
p
p
2
2
2
j
j
j
..
..
..
..
.
.
.
.
mp
mp
mp
j
j
j
p
If we multiply the th column for = 1, 2, , p 1 by m /mp ,
respectively, and then add the results to the pth column, we obtain the
following result on the th row in the pth column
X
1
D, (Ri Rj ) = 0
m mp j
for = x, y, z, where we have made use of the property of D, (Ri Rj )
in Eq. (1.20). Therefore, the last three columns of D(0) have been brought
to zero through the elementary column operations to matrix D(0). After
this, no additional columns can be brought to zero because of the absence
of Dp, (Ri Rj ) for = x, y, z in matrix D(0). Therefore, the rank of
D(0) is 3p 3. This implies that three acoustical branches are present in a
three-dimensional crystal with a p-atom basis and that the remaining 3p 3
branches are optical branches. This conclusion is verified in Fig. 1.2 by
the experimental results of inelastic neutron scattering on an NaCl crystal
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16
that has a two-ion basis. Figure 1.2 shows that NaCl has three acoustical
branches (one longitudinal and two transverse acoustical branches, that
is, one LA branch and two TA branches) and three optical branches (one
longitudinal and two transverse optical branches, that is, one LO branch
and two TO branches). Note that the two transverse acoustical branches
are degenerate along the directions (, 0, 0) and (, , ) and so are the two
transverse optical normal modes.
LO
30
h ( meV )
LO
LO
TO1
2TO
20
2TO
TO2
LA
LA
2TA
10
(, 0,0)
LA
TA2
2TA
TA1
(,, 0)
(,, )
0.5
Fig. 1.2 Dispersion relations of the normal modes in an NaCl crystal at 80 K. The
symbols denote experimental data of inelastic neutron scattering by Raunio et. al. [G.
Raunio, L. Almqvist, and R. Stedman, Physical Review 178, 1496 (1969)]. The lines
represent cubic-spline interpolations of the experimental data.
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Lattice Dynamics
1.3.4
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Polarization vectors
Q(s)
(k, ks ) = Q(k, ks ) (k)
(s)
(s)
(s)
(1.35)
(s)
and demand that the vector (k) = (1 (k), 2 (k), 3 (k)) be normalized. Inserting the above expression into Eq. (1.27) and specializing
(s)
Eq. (1.27) for branch s, we obtain the equations for (k)s
X
(s)
2
D, (k) ks
(k) = 0.
(1.36)
(s)
(k)
The vector
is referred to as the polarization vector of normal
mode ks on atom . The polarization vectors possess the following properties
(s)
(k) = (s)
(k),
X
(s0 )
(s)
(k) (k) = ss0 ,
(1.37)
(1.38)
(s)
(s)
(k) (k) = .
(1.39)
Equation (1.37) indicates that the effect of taking the complex conjugation
of a polarization vector is equivalent to taking the inversion of its wavevector variable k in k-space. Eq. (1.38) gives us the orthonormality relation
of polarization vectors. Eq. (1.39) gives us the completeness relation of
polarization vectors.
1.3.5
Displacements of atoms
We can derive an expression for the displacement of an atom in a threedimensional crystal with a multi-atom basis from Eqs. (1.23), (1.32),
and (1.35). We have
X
1
ikRj
uj, (t) =
qks (t)(s)
,
(1.40)
(k)e
N m ks
where qks (t)s are the generalized coordinates of normal modes, referred to
as the normal coordinates, and are given by
qks (t) = Q(k, ks )eiks t + Q(k, ks )eiks t .
(1.41)
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qks
(t) = qks (t).
1.3.6
(1.42)
To derive the Hamiltonian for a monatomic crystal, we first express its kinetic and interaction potential energies in terms of the above-introduced
normal coordinates. Making use of the expression of the displacement
uj, (t) of an atom in Eq. (1.40), we have for the kinetic energy
X1
1 X X
(s0 )
0 i(k+k0 )Rj
T =
qks (t)qk0 s0 (t)(s)
m u 2j, (t) =
(k) (k )e
2
2N 0 0 j
j
kk ss
1 XX
1X
(s0 )
=
qks (t)qks (t),
qks (t)qks0 (t)(s)
(k) (k) =
2
2
0
kss
(1.43)
ks
(1.45)
ks
To obtain the Hamiltonian of the crystal, we must first find the momentum
conjugate to qks (t). Differentiating L with respect to qks (t), we have
X
L
1
pks (t) =
=
qk0 s0 (t)qk0 s0 (t)
qks (t)
2 qks (t) 0 0
ks
1 X
=
qk0 s0 (t)k0 k s0 s + qk0 s0 (t)k0 k s0 s
2 0 0
ks
(1.46)
The Hamiltonian of the crystal then follows from the above Lagrangian in
the standard way
X
pks (t)qks (t) L
H=
ks
1X 2
1X
pks (t)pks (t) +
ks qks (t)qks (t).
=
2
2
ks
ks
(1.47)
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19
Lattice Dynamics
1.4
For the computation of the lattice specific heat, we first evaluate the internal
energy u per unit volume of the crystal. The internal energy is given by
the sum of the energies of individual harmonic oscillators weighted by the
H
Boltzmann
/Z with = 1/kB T the inverse of temperature and
R Q factor e H
Z =
dq
dp
e
the canonical partition function. The internal
ks
ks
ks
energy per unit volume is then given by
Z Y
1
u=
dqks dpks HeH
ZV
ks
Z Y
1
1 ln Z
=
dqks dpks eH =
.
(1.48)
ZV
V
ks
Our problem then reduces to the evaluation of Z. Making use of Eq. (1.47),
we have
Z Y
P
Z=
dqks dpks e ks (pks pks +ks qks qks )/2
ks
YZ
ks
The above maneuvers have reduced a 6pN -fold integral into a product
1
3pN
YZ
ks
0 0
0 0
0
dqks
dp0ks e(pks pks +ks qks qks )/2 =
3pN
A
,
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(1.49)
u
= 3pnkB ,
(1.50)
T
where p is the number of atoms in a primitive cell and n = N/V is the number of primitive cells per unit volume. For a three-dimensional monatomic
crystal without a multi-atom basis, p = 1. We then have cv = 3nkB . The
result in Eq. (1.50) is the well-known DulongPetit law for the lattice specific heat of solids. Expressing it in joules per kelvin per mole, we have
cv = 3R with R the gas constant, R = 8.314 JK1 mol1 . Expressing it
in calories per kelvin per mole, we have cv = 3R 6 calK1 mol1 with
R 1.986 calK1 mol1 .
Unfortunately, the result in Eq. (1.50) is in consistency with the experiment only in the high-temperature limit. While the above result indicates
that cv is a constant at all temperatures, the experiment reveals that cv
tends to zero essentially in the cubic power of T as T goes to zero. Therefore, classical theory of lattice vibrations is insufficient in explaining the
temperature dependence of the lattice specific heat. To resolve this inconsistency, we now quantize the lattice vibrations.
cv =
1.5
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Lattice Dynamics
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21
The first quantization is achieved by replacing the classical normal coordinates qks in Eq. (1.41) and the corresponding momenta pks of normal
modes by operators qks and pks that are required to satisfy the commutation relations
qks , pk0 s0 = kk0 ss0 , qks , qk0 s0 = pks , pk0 s0 = 0.
(1.51)
Note that qks and pks have the following properties
qks
= qks , pks = pks .
(1.52)
In the framework of the first quantization, the atomic displacements
and the Hamiltonian of the crystal corresponding to Eqs. (1.40) and (1.47),
respectively, are given by
X
1
ikRj
u
j, =
qks (s)
,
(1.53)
(k)e
N m ks
X
1X 2
=1
pks pks +
ks qks qks .
(1.54)
H
2
2
ks
ks
i
ks
a
ks =
qks
pks .
2~
ks
The operators a
ks and a
satisfy the following commutation relations
ks
a
ks , a
k0 s0 = kk0 ss0 ,
(1.56)
k0 s0 = 0.
a
ks , a
k0 s0 = a
ks , a
Inverting the expressions in Eq. (1.55), we can express qks and pks as
follows
1/2
~
qks =
a
ks + a
ks ,
2ks
(1.57)
1/2
~ks
a
ks a
ks .
pks = i
2
In terms of the annihilation and creation operators of phonons, the
quantum field operator of the atomic displacements and the Hamiltonian
of the crystal are given by
1/2
X
~
(1.58)
(s)
ks + a
ks eikRj ,
uj, =
(k) a
2N m ks
ks
X
=
H
~ks a
ks a
ks + 1/2 .
(1.59)
ks
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22
are given
The eigenvalues and eigenstates of the crystal Hamiltonian H
by
En =
(nks + 1/2)~ks ,
ks
|ni =
Y
ks
|nks i =
Y
ks
nks
1
|0i,
nks ! ks
(1.60)
(1.61)
i(kRj ks t)
+ (s)
a
ks .
(k)e
(1.62)
1.5.1
ks
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Lattice Dynamics
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23
1
(1.63)
e~ks /kB T 1
which is just what the BoseEinstein statistics gives for phonons. Note
that, because phonons in a crystal are constantly annihilated and created,
their number is not conserved and their chemical potential is zero.
hnks i =
1.6
ks
Z
=
d g()F (),
(1.64)
where g() is the phonon density of states, with g()d the number of
phonon states per unit volume in the frequency range from to + d,
and is given by
X Z dk
1 X
( ks ).
(1.65)
( ks ) =
g() =
V
(2)3
s
ks
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24
(1.66)
g() is then the summation of gs () over phonon branches. We can also express the phonon density of states in terms of an integral over the constantfrequency surface. To obtain this expression, we write dk = ddk with
d the area element on the constant-frequency surface S , ks = , and
express ( ks ) in terms of the component k of k perpendicular to the
constant-frequency surface S
(k k 0 )
,
( ks ) =
k ks
where k ks is the derivative in the direction of the normal of the constantfrequency surface S . We then have
Z
Z
Z
dk (k k 0 )
d
1
=
.
d
gs () =
(1.67)
(2)3 k ks
(2)3 S k ks
S
This alternative expression of the phonon density of states can differentiate the importance in the contributions of various normal modes to the
density of states and disclose the singularities in the dispersion relations.
If k ks = 0 at some particular wave vector k0 , this expression indicates
that the vicinity around k0 makes an important contribution to the phonon
density of states since the integrand diverges at k0 . This leads to a peak
in the phonon density of states at the corresponding frequency. Such a
frequency is known as a van Hove singularity. The wave vectors that contribute to van Hove singularities are referred to as critical points of the first
Brillouin zone.
1.7
Since lattice vibrations (phonons) contribute to a variety of physical properties of solids, the results obtained in the previous section find their extensive
applications in these properties. Here we concentrate on the phonon contribution to the specific heat (the lattice specific heat) of solids since the
specific heat of solids is one of the few problems that first gave us hints on
the inaccuracy of the classical theory in its description of the microscopic
world.
We will first derive a general expression for the lattice specific heat using
the eigenvalues of the crystal Hamiltonian in Eq. (1.60). We will then study
the Debye and Einstein models for the lattice specific heat.
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11:38
Lattice Dynamics
1.7.1
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25
High-temperature limit
11:38
26
terms are much smaller than the contribution from the first term because
~ks /kB T 1 and they are quantum corrections to the result from the
first term alone. Retaining only the first term in the above expansion, we
have
Z
X
kB T
dk
lim cv
~ks
T
T s
(2)3
~ks
X Z dk
= kB
= 3pkB /vc = 3pnkB ,
(1.70)
(2)3
s
where n = 1/vc = N/V is the number of primitive cells per unit volume
and p the number of atoms in a primitive cell. For a three-dimensional
monatomic crystal without a multi-atom basis, we have cv = 3nkB . The
result in Eq. (1.70) is just the DulongPetit law and it indicates that the
DulongPetit law is valid only at high temperatures.
1.7.3
Low-temperature limit
At low temperatures, the probabilities for the normal modes of high frequencies to be occupied by phonons are extremely small. Thus, we can take
only the normal modes of low frequencies into account in the computation
of the lattice specific heat at low temperatures. Since the optical normal
modes are of high frequencies in comparison with the acoustical phonons,
their contributions are neglected. For the acoustical normal modes, only
those of low frequencies make substantial contributions. From the computations of the dispersion relations of the normal modes in the last chapter,
we know that the dispersion relation for acoustical normal modes of low
frequencies can be well approximated by a linear dependence on the wave
cs (k)k/k
BT
Because e
becomes even smaller for large values of k, the error
introduced by extending the k-integration in Eq. (1.69) from over the first
Brillouin zone to over the entire reciprocal space is negligibly small at low
temperatures. We thus extend the region of the k-integration in Eq. (1.69)
to the entire reciprocal space. With the above-introduced simplifications,
the lattice specific heat of a solid at low temperatures is given by
Z
Z
3
1 X dk
~cs (k)k
dk
lim cv
T 0
BT 1
22 T s
4 0
e~cs (k)k/k
3 Z
6 kB T
x3
kB
,
= 2
dx x
~c
e 1
0
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11:38
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27
Lattice Dynamics
where
1
1X
=
3
c
3 s
dk 1
4 c3s (k)
(1.71)
is the average of the inverse of the cubed speeds of sound of the normal
modes of the three acoustical branches. The remaining integral can be
performed by first multiplying the numerator and denominator by ex and
then expanding 1/(1 ex ) as a Taylor series
6
lim cv 2
T 0
6
2
6
= 2
kB T
~c
3
x3 ex
1 ex
kB
kB T
~c
3
kB
Z
X
kB T
~c
3
6
22
kB
=
n4
5
n=1
dx
n=1
dx x3 enx
kB T
~c
3
kB ,
(1.72)
P
4
4
where we have made use of
n=1 1/n = 90/ . This is a remarkable
result! It implies that the lattice specific heat tends to zero cubically as
the temperature goes to zero, in excellent agreement with the experiment.
The problem of the lattice specific heat at low temperatures has thus been
solved with the quantization of lattice vibrations! The experimental data
of the specific heat of diamond at low temperatures are given in Fig. 1.3
together with a fit to cv = AT 3 .
cv ( calK -1 mol -1 )
0.03
0.02
0.01
0.0
0
20
40
T [K]
60
80
Fig. 1.3 Low-temperature specific heat of diamond. The open circles represent the
experimental data [W. DeSorbo, Journal of Chemical Physics 21, 876 (1953)]. The solid
line is a fit to cv = AT 3 with A = 4.774 108 calK4 mol1 .
11:38
28
Debye Model
3 2
() (D ),
=
22 c3
(1.73)
where (x) is the step function, (x) = 1 for x > 0, = 0 for x < 0. Note
that the phonon density of states in the Debye model is quadratic in for
0 < 6 D (this is a characteristic of the Debye model) and that it is zero
for < 0 or > D .
We now find expressions for kD and D . For a three-dimensional
monatomic crystal without a multi-atom basis, the total number of acoustical normal modes is 3N with N the number of primitive cells.
R The number
of acoustical normal modes in the Debye model is given by V d gD ().
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11:38
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29
Lattice Dynamics
We thus have
Z
3V
d gD () =
3N = V
d 2 () (D )
22 c3
Z D
3
3V
D
V
2
=
d
=
(1.74)
2
3
2
2 c 0
2 c3
Z
1/3
c, kD = 62 n
1/3
(1.75)
3
22 T
= 9nkB
kD
dk
~ck 3
e~ck/kB T
1
3 Z D /T
T
x3
dx x
,
T
D
e 1
0
(1.76)
High-temperature limit
In the high-temperature limit, since D /T 1, the values of the integration variable x are very small in the entire integration interval. We can then
expand the exponential function ex in the denominator of the integrand in
Eq. (1.76) as a Taylor series and retain only the first two terms. We then
have
cD
v = 9nkB
T
D
3 Z
T
D /T
dx x2
= 3nkB .
(1.77)
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30
1.8.2
Low-temperature limit
Since D /T 1 in this limit, the upper limit of the integral in Eq. (1.76)
can be extended to infinity. We then have
3 Z
x3
T
cD
=
9nk
T
dx
B
v
T
D
ex 1
0
3
3
124 T
T
=
nkB 234
nkB ,
(1.78)
5
D
D
where the result for the integral in Eq. (1.72) has been used. Hence, the
lattice specific heat at low temperatures also follows the T 3 -power law in
the Debye model. The success of the Debye model at low temperatures lies
at the physical fact that only low-frequency acoustical single-phonon states
are occupied with appreciable probabilities at low temperatures.
1.8.3
Debye temperature
As mentioned in the above, the Debye temperature has been used to characterize a solid. As a matter of fact, it is one of the most important characteristics of a solid. It reflects the density, structural stability, and bonding
strength of the solid. Structure defects in a solid can be also identified
through the variation in its Debye temperature. The Debye temperature
is also the characteristic energy scale of phonons in the solid and used in
comparison of energy scales with other elementary excitations. The magnitudes of the Debye temperature vary widely among solids: It can be as
large as over 2, 000 K, such as in diamond, and as small as below 40 K,
such as in cesium. The typical value of the Debye temperature D can be
taken as several hundred Kelvins. Since the Fermi temperature F of the
electron gas in a metal is typically several ten thousand Kelvins, the ratio
D /F is typically of the order of 102 . Thus, the energy scale of phonons
in a metal is very small compared to that of electrons. This fact will be
extensively exploited in the study of the electronphonon interaction.
The Debye temperature of a solid can be inferred from several different
physical quantities of the solid, such as the entropy, the specific heat, the
speed of sound, the elastic constants, and etc.
The Debye temperature of a solid in general varies with temperature.
The variation is large in some solids and small in others. The temperature dependence of the Debye temperature of a perfect crystalline solid is
chiefly caused by the electronphonon interaction and the anharmonicity
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11:38
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31
Lattice Dynamics
in lattice vibrations. The temperature dependence of the Debye temperature in diamond is shown in Fig. 1.4 from which it is seen that the Debye
temperature in diamond is high and that its variation is large. The Debye
temperature peaks at about 60 K with a peak value of about 2, 250 K. It is
about 1, 850 K at 25 K and 1, 870 K at 300 K. The large Debye temperature
in diamond leads to a small lattice specific heat in diamond as shown in
Fig. 1.3.
2300
2200
D [K ]
2100
2000
1900
100
200
300
T [K]
Fig. 1.4 Debye temperature as a function of temperature in diamond [W. DeSorbo,
Journal of Chemical Physics 21, 876 (1953)].
The Debye temperatures of alkali metals are small compared to the Debye temperature of diamond, with lithium having the largest Debye temperature (about 375 K) among the alkali metals and its Debye temperature not
varying appreciably with temperature. The Debye temperatures of the remaining alkali metals, sodium, potassium, rubidium, and cesium, are shown
in Fig. 1.5 as functions of temperature. It is seen the Debye temperatures
of these alkali metals do not vary much with temperature, either.
1.9
Einstein Model
kB X
kB X (~ks /2kB T )2
=
E(~ks /2kB T ),
2
V
V
sinh (~ks /2kB T )
ks
ks
(1.79)
11:38
32
150
D [ K ]
100
50
10
100
200 300
T [K]
Fig. 1.5 Debye temperature as a function of temperature for alkali metals Na, K, Rb,
and Cs (from top to bottom) from T = 1 to 300 K [D. L. Martin Physical Review 139,
150 (1965)].
x2
.
sinh2 (x)
(1.80)
The function E(x) is called the Einstein function. For the convenient evaluation of the contribution of the optical phonons to the lattice specific
heat, Einstein treated the optical normal modes as independent harmonic
oscillators and assumed that they have the identical frequency E . This is
the well-known Einstein model for the lattice specific heat. Note that the
acoustical phonons are not taken into account in the Einstein model. Because the optical phonons all have nonzero frequencies, the lattice specific
heat given by the Einstein model has an incorrect temperature dependence
at low temperatures.
The lattice specific heat per unit volume in the Einstein model is simply
given by
cE
v =
popt N kB
(E /T )2 eE /T
E(~E /2kB T ) = popt nkB
2 ,
V
eE /T 1
(1.81)
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11:38
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33
Lattice Dynamics
agrees with that given by the DulongPetit law and with that given by the
Debye model.
The temperature dependence of the lattice specific heats predicted
by the Debye and Einstein models are plotted in Fig. 1.6. For the lattice specific heat given by the Debye model, cv /3nkB is plotted, whereas
cE
v /popt nkB is plotted for the Einstein model.
1.0
Debye
0.5
Einstein
0.0
0.0
0.5
1.0
1.5
T D , T E
Fig. 1.6 Lattice specific heats predicted in the Debye and Einstein models as functions
of reduced temperature T /D or T /E . The solid line is for cD
v and the dashed line for
cE
v.
From Fig. 1.6, it is seen that the lattice specific heats from the Debye
and Einstein models both tends to zero as temperature goes to zero and
approach the result given by the DulongPetit law at high temperatures.
D
E
Overall, cE
v is smaller than cv . Note that cv goes to zero much faster than
E
cD
v does. This is due to the erroneous behavior of cv at low temperatures
mentioned in the above.
1.10
11:38
34
is defined by
(T ) =
BT
,
cv
(1.82)
ks
ks
Here the eigenvalues of the crystal Hamiltonian in Eq. (1.60) have been
used. The Gr
uneisen parameter is then given by
1 F
kB
ln Z
(T ) =
=
T
cv T V T V
cv T
V
T V
X
ks E(~ks /2kB T )
=
ks
E(~ks /2kB T )
(1.84)
ks
where the Einstein function E(x) is given in Eq. (1.80) and ks is the mode
Gr
uneisen parameter for normal mode ks and is given by
ln ks
.
(1.85)
ln V
Note that Eq. (1.84) implies that (T ) is a weighted average of the mode
Gr
uneisen parameters with the weight for normal mode ks given by the norP
malized Einstein function: E(~ks /2kB T ) divided by ks E(~ks /2kB T ).
For a one-dimensional crystal, the mode Gr
uneisen parameter is given
by
ks =
ln ks
(1.86)
ln L
with L the length of the one-dimensional crystal. Take a one-dimensional
crystal of inert gas atoms of mass m as an example. The phonon dispersion
relation is given by k = (4K/m)1/2 | sin(ka/2)| for such a one-dimensional
crystal, where K is the force constant. We have
ks =
k =
ln k
= (ka/2) cot(ka/2).
ln a
(1.87)
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35
Lattice Dynamics
E(~k /2kB T )
(1.88)
The values of (T ) at a number of temperatures are evaluated numerically with the results plotted in Fig. 1.7 as a function of T / with
= ~(4K/m)1/2 /kB .
-0.7
-0.8
-0.9
-1.0
0.0
0.5
1.0
T
Fig. 1.7 Plot of the Gr
uneisen parameter of a one-dimensional crystal of inert gas atoms
as a function of the reduced temperature T /.
1.11
The specific heat of a pure metallic crystal consists of the electronic and
lattice specific heats. At low temperatures, the electronic specific heat takes
on the form cev = T with the electronic specific heat coefficient and the
3
lattice specific heat takes on the form cL
v = AT [cf. Eqs. (1.72) and (1.78)].
Thus, the specific heat of a pure metal is given by
3
cv = cev + cL
v = T + AT .
(1.89)
11:38
36
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cv T [ mcalK -2 mol -1 ]
cv [ m calK -1 mol -1 ]
(a)
0.8
0.4
0.0
0
0.5
1.0
1.5
0.6
(b)
0.5
0.4
0.3
0.0
0.5
T [K]
1.0
2
1.5
2.0
2.5
T [K ]
Fig. 1.8 Low-temperature specific heat of sodium. (a) Specific heat cv as a function of
temperature T . The open circles represent the experimental data [D. L. Martin, Physical
Review 124, 438 (1961)]. The solid line is a linear least-squares fit of the experimental
data to cv = T + AT 3 . (b) Specific heat divided by temperature, cv /T , as a function
of T 2 . The open circles represent the same experimental data as in (a) but now cv /T
is plotted as a function of T 2 . The solid straight line is a linear least-squares fit of the
experimental data to cv /T = + AT 2 .
To see how well the form of the low-temperature specific heat in Eq. (1.89)
is obeyed in a real simple metal, we show the low-temperature specific heat
of sodium in Fig. 1.8.
In Fig. 1.8(a), the experimental data of the low-temperature specific
heat of sodium are shown. From the linear least-squares fit of the experimental data to the expression in Eq. (1.89), it is seen that the lowtemperature specific heat of sodium does follow the law prescribed in
Eq. (1.89). Although the coefficients and A can be determined from
the above linear least-squares fit of the experimental data, it has become a custom that the coefficients are determined by plotting the experimental data in the manner of cv /T versus T 2 . Such a plot is shown
in Fig. 1.8(b) together with the linear least-squares fit of the experimental data to cv /T = + AT 2 . In such a plot, the intercept on the vertical axis yields the value for and the slope of the straight line gives
the value for A. It has been found that 0.335 mcalK2 mol1 and
A 0.107 mcalK4 mol1 .
The above example demonstrates that the low-temperature specific heat
of a simple metal follows the law given in Eq. (1.89). However, deviations
from this law are observed in metallic compounds, especially in metallic
compounds that contain d or f elements, such as heavy fermion systems5 .
5 G.
11:38
PROBLEMS
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37
Problems
1-1 Consider a linear chain in which alternate ions have masses m1 and
m2 and only nearest neighbors interact through a spring of force
constant K. Find the dispersion relations for the normal modes.
Discuss the limiting cases for m1 m2 and m1 = m2 .
1-2 A commonly-seen example of a simple one-dimensional crystal is a
line of point masses, each of which has two nearest neighbors: One
is distance d away and the other distance (a d) away (d a)
in equilibrium. The two neighboring point masses are connected by
springs, with the force constants of the springs between the neardistanced point masses and between the far-distanced point masses
given by K and G (K > G), respectively.
(1) Write down the harmonic crystal potential energy in terms of the
displacements of point masses from their equilibrium positions.
(2) Set up the classical equations of motion for the point masses.
(3) Solve for the frequencies and polarization vectors of the normal
modes of the lattice vibrations from the classical equations of
motion.
1-3 Consider a one-dimensional crystal of atoms of mass m. Only the
interactions up to the next nearest neighbors are taken into account
and are modeled by springs with the force constant for the nearestneighbor interaction given by K and that for the next-nearestneighbor interaction given by G.
(1) Compute the dispersion relation of the normal modes.
(2) Find the condition on G so that the dispersion curve peaks inside
the first Brillouin zone.
(3) Find the expressions for the group and phase velocities and evaluate them at the peak position of the dispersion curve under the
condition found in (2).
1-4 Consider a linear chain of atoms of mass m with the nearest neighboring atoms connected by springs of force constant K. In addition,
the motion of each atom is damped, with the damping force u j
exerted on the jth atom, where uj is the displacement of the jth
atom from its equilibrium position. Assume that (mK)1/2 .
(1) Write down the equations of motion of atoms with the damping
taken into account.
11:38
38
ky
/a
/a
Z
/a
kx
X
/a
Fig. 1.9 First Brillouin zone of the two-dimensional square lattice. Three highsymmetry points, , X, and M , and three high-symmetry lines, , , and Z, are
shown.
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11:38
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39
PROBLEMS
(ij)
where hiji indicates summation over the nearest neighbors and (ij)
summation over the next nearest neighbors. Here a is the lattice
~ i s are Bravais lattice vectors, and ~ui s are deviations of
constant, R
atoms from their equilibrium positions.
(1) Construct the dynamical matrix.
(2) Find the frequencies and polarization vectors of normal modes
along the lines , , and Z, respectively.
(3) Plot the dispersion relations along these three high-symmetry
lines.
1-8 The lattice dynamics of a simple cubic crystal of lattice constant a
and atom mass M is studied here with only interactions between
nearest-neighboring atoms taken into account. The interactions are
modeled as being mediated through springs of force constant .
(1) Write down the potential energy of the crystal and construct the
dynamical matrix.
(2) Solve for the dispersion relations.
(3) Plot the dispersion relations along [100] and label branches properly. Give the physical reason for the zero-frequency normalmode branches.
(4) Indicate the pattern of displacements of eight atoms in the conventional cell for the mode at k = (/a, 0, /a) with displacements along ex .
11:38
40
L = 2(2K/M )1/2 sin(ka/4) and the frequency of the two degenerate transverse acoustical normal modes is given by T =
2(K/M )1/2 sin(ka/4). Also consider the cases for k in the [110]
and [111] directions
1-10 A three-dimensional crystal has a two-atom basis. The masses of the
two atoms in the basis are m1 and m2 , respectively. Let v1 and v2 be
their velocities. Show that, for an optical normal mode at the center
of the first Brillouin zone (k = 0), m1 v1 + m2 v2 = 0.
1-11 The quantum field operator of atomic displacements for a threedimensional crystal with a multi-atom basis is given in Eq. (1.62).
We now derive the quantum field operator of atomic momenta. In
analogy with the definition of momentum in classical mechanics, let
Pj, (t) = m u
j, (t)/t.
(1) Write down the explicit expression of Pj, (t) in terms of operators a
ks and a
ks .
(2) Show that [
uj, (t), P`, (t)] = i~j` . Therefore, Pj, (t)
is the momentum field operator conjugate to the displacement
field operator u
j, (t).
(3) Show that u
j, (t) and Pj, (t) are Hermitian operators.
1-12 In this problem, the Hamiltonian for a three-dimensional crystal with
a multi-atom basis will be derived.
(1) Specializing the above-obtained expression for Pj, (t) to the
time-independent case and making use of the resultant expression, express the kinetic energy of the crystal, T =
P
ks and a
ks .
j, Pj, Pj, /2m in terms of operators a
(2) Using the expression of uj, , express the harmonic lattice po harm = (1/2) P P
tential energy of the crystal,
j,
j`
, u
D, (Rj R` )
u`, in terms of operators a
ks and a
ks .
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11:38
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41
PROBLEMS
(2) From the thermodynamic relation S = F/T V , compute
the entropy S.
(3) Express S in terms of the thermal average of the occupation
number nB (~ks ) hnks i of the single-phonon state |ksi.
1-14 Consider a one-dimensional crystal of inert gas atoms. Let L be the
length of the crystal and N the number of atoms. Let a be the
lattice constant. (i) Evaluate the phonon density of states for this
crystal. (ii) Derive an integral expression for the lattice specific heat
of the crystal. (iii) Evaluate the lattice specific heat in the high- and
low-temperature limits.
1-15 Reconsider the above problem within the Debye model. (i) Find the
phonon density of states within the Debye model. (ii) Determine the
Debye frequency. iii. Find a general expression for the lattice specific
heat. (iv ) Evaluate the lattice specific heat in the high- and lowtemperature limits. (v ) Compare the exact and Debye results for the
lattice specific heat by plotting them together from zero temperature
to the Debye temperature.
1-16 Consider the relative size of the electronic and lattice contributions
to the specific heat of a metal using the Sommerfeld theory for the
electrons and the Debye model for the phonons. (i) Find an expres
sion for the ratio cev /cL
v . (ii) Determine the temperature T at which
e
L
cv = cv . (iii) Give an estimate on the order of magnitude for T in
alkali metals.
1-17 A number of values of the specific heat of potassium at low temperatures are given in Table 1.1. (i) Plot Cv versus T and Cv /T versus
T 2 . (ii) Perform a linear least-squares fit of the experimental data
for Cv /T to Cv /T = + AT 2 and determine and A. (iii) Estimate
the Debye temperature of potassium at low temperatures.
Table 1.1 Low-temperature specific heat of potassium in mJ K1 mol1 [W. H. Lien
and N. E. Phillips, Physical Review 133, A1370 (1964)]. The temperature T is in K.
T
0.260
0.278
0.295
0.250
0.265
0.269
4
1
3
1
0
8
Cv
0.585
0.630
0.678
0.559
0.596
0.606
2
6
6
2
9
6
T
0.288
0.289
0.306
0.327
0.337
0.347
5
4
7
0
9
8
Cv
0.657
0.665
0.710
0.768
0.796
0.836
8
7
4
7
2
2
T
0.364
0.373
0.393
0.399
0.423
0.427
4
4
5
4
1
4
Cv
0.885
0.918
0.973
1.003
1.021
1.102
8
0
3
0
0
0
T
0.451
0.457
0.483
0.496
0.543
0.594
5
8
5
9
5
4
Cv
1.177
1.208
1.302
1.353
1.551
1.786
0
0
0
0
0
0
11:38
42
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