TWO ATOMS PER PRIMITIVE BASIS

The phonon dispersion relation shows new features in crystals with two or more atoms per primitive
basis. Consider, for example, the NaCl or diamond structures, with two atoms in the primitive cell.
For each polarization mode in a given propagation direction the dispersion relation w versus K
develops two branches, known as the acoustical and optical branches, as in Fig. 7. We have
longitudinal LA and transverse acoustical TA modes, and longitudinal L0 and transverse optical T0
modes.

If there are p atoms in the primitive cell, there are 3p branches to the dispersion relation: 3
acoustical branches and 3p 3 optical branches. Thus germanium (Fig. 83) and KBr (Fig. 8b), each with
two atoms in a primitive cell, have six branches: one LA, one LO, two TA, and two TO.

The numerology of the branches follows from the number of degrees of free dam of the atoms. with
p atoms in the primitive cell and N primitive cells, there are pN atoms. Each atom has three degrees
of freedom, one for each of the x, y, z directions, making a total of 3pN degrees of freedom for the
crystal. The number of allowed K values in a singie branch is just N for one Bn'llouin zone. Thus the

we show in Chapter 5 by application of periodic boundary conditions to the modes of the crystal of
volume V that theme is one K value in the volume (211)3/V in Fourier space. The volume of a
Brillouin zone is (217)3/V, where V‘ b the volume of a crystal prinurive cell. Thus the number of
Illowcd K values in a Brillouin zone is V/Vt. which is just N, the number of primitwe cells in the
crystal.

Figure 9 A diatomic crystal structure with masses M1. M2 connected by force constant C between
adjacent planes. The displacements of atoms M. are denoted by 11,1, u,, "nl. . . , and of atoms M2 hv
v,_., 0,, 0,“. The repeat distance is a in the direction of the wavevector K. The atoms are shown in
their undisplaced positions.

LA and the two TA branches have a total of 3N modes, thereby accounting for 3N of the total
degrees of freedom. The remaining (3p 3)N degrees of freedom are accommodated by the optical
branches.

We consider a cubic crystal where atoms of mass M 1 lie on one set of planes and atoms of mass M2
lie on planes interleaved between those of the first set (Fig. 9). It is not essential that the masses be
different, but either the force constants or the masses will be different if the two atoms of the basis
are in nonequivalent sites. Let a denote the repeat distance of the lattice in the direction normal to
the lattice planes considered. We treat waves that propagate in a symmetry direction such that a
single plane contains only a single type of ion; such directions are [111] in the NaCl structure and
[100] in the CsCI structure.
We write the equations of motion under the assumption that each plane interacts only with its
nearest-neighbor planes and that the force constants are identical between all pairs of nearest-
neighbor planes. We refer to F ig. 9 to obtain

Ml dz“: = C(Ov + 01-1 2a,) ;

dtz

(120 (18) M2 dt; : C(u1+l + u: 201)

We look for a solution in the form of a traveling wave, now with different amplitudes u, v on
alternate planes:

u. = u exp(Ls‘Ka) exp(-iwt) ; 02 = v exp(isKa) exp(-iwt) . (19)

We define a in Fig. 9 as the distance between nearest identical planes, not nearest-neighbor planes.
On substitution of(19) in (18) we have

2Mlu = Cv[l + exp(-iKa)] 2Cu ;

-w2Mzu = Cu[exp(iKa) + l] 2C0 . (20)

The homogeneous linear equations have a solutian only If the determinant of the coefficients of the
unknowns u, o vanishes:

20 M,u’ -C[1 + (4Ka)] a o (21) --C[l +elp(iKa)] 2C-M ' or u.M,u‘ 20m, + uga’ + 2C’(l cos Kn) = o . (22)

We can solve this equation exactly for w‘. but it Is simpler to enmine the limiting cases Kn < l and Ka
= :1 at the zone boundary. For small Ka we

havecosKaill-5K’a'+...,andthetworootsare
~s.2c(' Ti) (optical branch); (23) 2 50 a'M: + M'K'a‘ (Imam bunch) . (24)

The extent of the first Brillouin zone is -w/a S K s r/a_ where a is the repeat distance of the lattice. At
K__ = 21/0 the roots are

u’ zC/Ml ; u’ : 2cm, . (25)

The dependence of» on K is shown In Fig. 7 for M. > M, The particle displacements in the transverse
acoustical (TA) and transverse optical (TO) branches are shown in Fig. 10. For the optical branch It K
0 we find, on substitution of (23) in (20),

uE

3 MI ' (25)

The atoms vibrate against each other. but their center of mass is fixed. If the two atoms carry
opposite charges, as in F ig. 10. we may excite a motion of this

type with the electric field of a light wave, so that the branch is called the opti cal branch. At a
general K the ratio 11/17 will be complex, as follows from either of the equations (20). Another
solution for the amplitude ratio at small K is u = 9, obtained as the K = 0 limit of (24). The atoms (and
their center of mass) move together, as in long wavelength acoustical vibrations, whence the term
acoustical branch.

Wavelike solutions do not exist for certain frequencies, here between (2C/Ml)”2 and (20/M2)V2.
This is a characteristic feature of elastic waves in polyatomic lattices. There is a frequency gap at the
boundary Km. = 1'1r/a of the first Brillouin zone.

QUANTIZATON OF ELASTIC WAVES

The energy of a lattice vibration is quantized. The quantum of energy is called a phonon in analogy
with the photon of the electromagnetic wave. The energy of an elastic mode of angular frequency w
is

c = (n + bin» (27)
when the mode is excited to quantum number n; that is, when the mode is occu pied by n phonons.
The term Hun is the zero point energy of the mode. It occurs for both phonons and photons as a
consequence of their equivalence to a quantum harmonic oscillator of frequency a), for which the
energy eigenvalues are also (n + th. The quantum theory of phonons is developed in Appendix C.

We can quantize the mean square phonon amplitude. Consider the stand ing wave mode of
amplitude

u=uoeostcosax.

Here u is the displacement of a volume element from its equilibrium position at x in the crystal. The
energy in the mode, as in any harmonic oscillator, is half kinetic energy and half potential energy,
when averaged over time. The kinetic energy density is ;p(&u/Bt)2, where p is the mass density. In a
crystal of volume V, the volume integral of the kinetic energy is :przug sin2 wt. The time aver~ age
kinetic energy is

ngw’uf, = ;(n + Dfuo , (28) because <sin2 wt> = ;. The square of the amplitude of the mode is u: = 4(n
+ 95/pr . (29)

This relates the displacement in a given mode to the phonon occupancy n of the mode.

What is the sign of w? The equations of motion such as (2) are equations for mg, and if this is
positive then m can have either sign, + or -. But the

energy of a phonon must be positive, so it is conventional and Suitable to view. in as positive. If the
crystal structure is unstable, then «:2 will be negative and w will be imaginary.

PHONON MOMENTUM

A phonon of wavevector K will interact with particles such as photons, neutrons. and electrons as if
it had a momentum hK. However. a phonon does not carry physical momentum.

The reason that phonons on a lattice do not carry momentum is that a phonon coordinate (except
for K = 0) involves relative coordinates of the atoms. Thus in an “2 molecule the internuclear
vibrational coordinate rl r; is a relative coordinate and does not carry linear momentum; the center
of mass coordinate g(r, + r2) corresponds to the uniform mode K = 0 and can carry linear
momentum.
In crystals there exist wavevector selection rules for allowed transitions between quantum states.
We saw in Chapter 2 that the elastic scattering of an x-ray photon by a crystal is governed by the
wavevector selection rule

k’=k+G, (30)

where C is a vector in the recipmcal lattice, k is the wavevector of the incident photon, and k' is the
wavevector of the scattered photon. In the reflection process the crystal as a whole will recoil with
momentum -flG, but this uniform mode momentum is rarely considered explicitly.

Equation (30) is an example of the mle that the total wavevector of interacting waves is conserved in
a periodic lattice, with the possible addition of a reciprocal lattice vector C. The true momentum of
the whole system always is rigorously conserved. If the scattering of the photon is inelastic, with the
creation of a phonon of wavevector K, then the wavevector selection rule becomes

k’+K-k+c. (31) [f a phonon K is absorbed in the process, we have instead the relation

k'-k+K+G. (32) Relations (31) and (32) are the natural extensions of (30).

INELASTIC SCATTERING BY PHONONS

Phonon dispersion relations u(K) are most often determined experimentally by the inelastic
scattering of neutrons with the emission or absorption of a phonon. A neutron sees the crystal
lattice chiefly by interaction with the nuclei

of the atoms. The kinematics of the scattering of a neutron beam by a crystal lattice are described by
the general wavevector selection rule:

k+G=k’:K, (33)

and by the requirement of conservation of energy. Here K is the wavevector of the phonon created
(+) or absorbed (-) in the scattering process, and G is any reciprocal lattice vector. For a phonon we
choose G such that K lies in the first Brillouin zone.
4 N 5 [001] .909 ° [110] . o ' [111] . . . . . “é .9 . --1 I 51 8° 3 0 o o o o o b 2 go o ° 5 ‘0 0 0° . 0
§olgongitudinal o o o k. OTrmsvetse 0 ° 00 100 0 n0 0 u!

Wavevector, in units 21r/a

Figure 11 The dispersion curves of sodium for phonons propagating in the [001], [110], and [l l 1]
directions at 90 K, as determined by inelastic scattering of neutrons, by Woods. Brockhouse. March
and Bowers.

The kinetic energy of the incident neutron is p2/2Mn. where M. is the mass of the neutron. The
momentum p is given by Ink, where It is the wavevector of the neutron. Thus hich/ZMn is the kinetic
energy of the incident neutron. If Ic’ is the wavevcctor of the scattered neutron, the energy of the
scattered neutron is h’k’2/2M,. The statement of conservation of energy is

2! 2:2 3-542; tau, (34)

where fun is the energy of the phonon created (+) or absorbed (-) in the process.

To determine the dispersion relation using (38) and (34) it is necessary in the experiment to find the
energy gain or loss of the scattered neutrons as a function of the scattering direction It li’. Results for
germanium and KBr are given in Fig. 8; results for sodium are given in Fig. 11. A spectrometer used
for phonon studies is shown in Fig. 12.

SUMMARY

The quantum unit of a crystal vibration is a phonon. If the angular frequency is w, the energy of the
phonon is fun.

o When a phonon of wavevector K is created by the inelastic scattering of a photon or neutron from
wavevector k to k', the wavevector selection rule that governs the process is

k = k’ + K + G , where G is a reciprocal lattice vector.

0 All elastic waves can be described by wavevectors that lie within the first Brillouin zone in
reciprocal space.
0 If there are p atoms in the primitive cell, the phonon dispersion relation will have 3 acoustical
phonon branches and 3p 3 optical phonon branches.

Problem 1. Monatotm'c linear lattice. Consider a longitudinal wave