Surface Vibrational Surface Vibrational Surface Vibrational Surface Vibrational

Properties Properties Properties Properties Properties Properties Properties Properties

Unlike surface crystallography, which deals with average positions of
atoms in a crystal, lattice dynamics (LD) extends the concept of
crystal lattice to an array of atoms with finite masses that are
capable of motion. This motion is not random but a coherent
superposition of vibrations of atoms around their equilibrium sites
due to the interaction with neighbor atoms. A collective vibration
of atoms in the crystal forms a wave with given wavelength and
amplitude.
Just as light is a wave motion that is considered as composed of
particles called photons, we can think of the normal modes of
vibration in a solid as being particle-like. The quantum of lattice
vibration is called the phonon. The problem of lattice dynamics is
to find the normal modes of vibration of a crystal and to calculate
their energies (or frequencies, ) as a function of their wavevector
k . The relationship (k) is called phonon dispersion .
LD offers two different ways of finding the dispersion relation:
Quantum-mechanical approach
Semiclassical treatment of lattice vibrations
There are two possible polarizations for the vibrations of atoms in a
crystal: longitudinal and transverse
In case of longitudinal modes the displacement of the atoms from
their equilibrium position coincides with the propagation direction of
the wave, whereas for transverse modes, atoms move perpendicular
to the propagation of the wave.
For one atom per unit cell the phonon dispersion curves are
represented only by acoustical branches. However, if we have more
than one atom in the unit cell optical branches will appear than one atom in the unit cell optical branches will appear
additionally.
The difference between acoustical and optical branches arises
because of the options for the vibration of the atoms in the unit cell.
For example, atoms A and B of diatomic cell can move together in
phase (acoustical branch) or out of phase (optical branch).
Generally, for N atoms per unit cell there will be 3 acoustical
branches (1 longitudinal and 2 transverse) and 3N-3 optical branches
(N-1 longitudinal and 2N-2 transverse)
Lets consider a linear chain of identical atoms of mass M spaced at a distance a,
the lattice constant, connected by Hook's law springs.
For simplicity we will consider longitudinal deformations - that is, displacements of
atoms are parallel to the chain.
Let U
n
=displacement of atom n from its equilibrium position
U
n-1
=displacement of atom n-1 from its equilibrium position
U
n+1
=displacement of atom n+1 from its equilibrium position
The force on atom n will be given by its displacement and the displacement of its
nearest neighbors :
Acoustical phonons Acoustical phonons Acoustical phonons Acoustical phonons
The equation of motion is:
where is a spring constant.
The right hand side is a second derivative with respect to space, so that we have
a differential equation of solution
with U
no
= U
o
amplitude of the wave.
If we substitute our trial wave solution into the equation of motion we find
a phonon's dispersion relation for linear monatomic chain as follows:
One important feature of the
dispersion curve is the periodicity of
the function. For unit cell length a ,
the repeat period is equal to the unit
cell length in the reciprocal lattice.
Therefore the useful information is
contained in the waves with wave
vectors lying between the limits
Optical phonons Optical phonons Optical phonons Optical phonons
Consider a lattice with two kinds of atoms - that is a lattice with a basis of
two atoms in the primitive cell. Now we have to write two solutions for the
displacement corresponding to the two masses m and M. The equations of
motion are:
We try solution like:
where A and B are the amplitudes of vibration of atom of mass m and M,
respectively. The diatomic case has two solutions of the dispersion
relation:
The methods to measure the dispersion relation of lattice vibrations are:
Bulk: Neutron Inelastic Scattering and Raman scattering of X-Rays
Surface: Electron Energy Loss Spectroscopy (EELS) and Inelastic He
Atom Scattering
BULK phonons
Neutron Inelastic Scattering
Thermal neutrons have an energy in the same range as the lattice Thermal neutrons have an energy in the same range as the lattice
vibrations and a wavelength of the same order as the crystal lattice spacing.
By analyzing the energy and direction of the scattered neutrons, the phonon
dispersion relation is obtained. Neutrons are well suited for bulk phonon
dispersion studies because of their very small cross section with matter
which allows them to penetrate deeply into the crystal.
More recently, inelastic X ray scattering has become available thanks to the
high flux obtained at synchrotron radiation sources. The photon energy has
to be high to match the wavevector transfer. The interaction mechanism is
Raman scattering
HREELS and He Atom Scattering HREELS and He Atom Scattering HREELS and He Atom Scattering HREELS and He Atom Scattering
HREELS and He atom inelastic scattering are currently employed to
study the dispersion of surface phonons.
The He atom measurements cover the region of energy transfers up to
about 30-50meV with a resolution down to 0.5-1meV.
HREELS measurements have no limit in the energy loss and can easily
access the high frequency range of light adsorbate modes (e.g O-H access the high frequency range of light adsorbate modes (e.g O-H
approx 500meV), albeit with the lower resolution of about 2-3 meV. Due
to the high cross section of the electrons with matter, ~5A
2
, their
penetration depth in HREELS experiments (kinetic energy from 20 to
200 eV) is about 2-3 surface layers. Multiple scattering phenomena can
be used to tune of particular modes.
He atoms, however, have lower kinetic energy (~0.05eV) and reflect at
relatively large distances, the order of 3-4 A
2
, from the surface plane.
Thus in general multiple interactions of the He atoms with the surface
are negligible.
Phonons Phonons Phonons Phonons are collective lattice vibration modes, and surface phonons surface phonons surface phonons surface phonons are those
particular modes associated with surfaces; they are an artifact of periodicity,
symmetry symmetry symmetry symmetry, and the termination of bulk crystal structure associated with the
surface layer of a solid [1]. The study of surface phonons provides valuable
insight into the surface structure and other properties specific to the surface
region, which often differ from bulk. The figure below gives a pictoral
representation of the atomic motion in a phonon mode.
Surface phonons are represented by a wave vector wave vector wave vector wave vector along the surface, q qq q, and an
energy corresponding to a particular vibrational mode frequency, [1]. The
surface surface surface surface Brillouin zone (SBZ Brillouin zone (SBZ Brillouin zone (SBZ Brillouin zone (SBZ) is two dimensional. For example, the face
centered cubic (100) surface is described by the directions X and M,
referring to the [110] direction and [100] direction, respectively [2].
Surface phonons Surface phonons Surface phonons Surface phonons
Surface phonon branches may occur in specific parts of the SBZ or
encompass it entirely across. These modes can show up both in the bulk
phonon dispersion bands, resonance, or run outside of these bands as a
pure surface phonon mode. Thus, surface phonons can be purely surface
existing vibrations, or simply the expression of bulk vibrations in the
presence of a surface, known as a surface-excess property.
A particular mode, the Rayleigh phonon mode, exists across the entire BZ
and is known by special characteristics, including a linear frequency versus
wave number relation near the SBZ center.
due to the very different masses, the motion of electrons and nuclei takes
place on very different time scales (femto- vs pico- seconds) so that
electrons follow the motion of the nuclei adjusting adiabatically to their
positions
The potential {r(n)} felt by an atom in the solid, depends therefore , to a
very good approximation only on the atomic coordinates {r(n)} .
To write the equation of motion, lets expand {r(n)} into a Taylor series
around the equilibrium positions {r
0
(n)}.
Born and Oppenheimer approximation Born and Oppenheimer approximation Born and Oppenheimer approximation Born and Oppenheimer approximation
around the equilibrium positions {r
0
(n)}.
The first derivative vanishes around the minimum and the other terms may
be neglected since the displacements u

(n) are small with respect to the

lattice spacing. Given M(n), the mass of the n
th
atom, we can write:
... ) ( ) (
) , ; , (
)}) ( ({ )} ( ({
, , ,
2
0 0
+


+ =





m n
m u n u
u u
m n
n r n r
r r

,
2
) (
) , ; , (
) ( ) (
m
m u
u u
m n
n u n M
& &
The sum extends over all atoms of the solid, but the coupling decreases
rapidly with distance. Considering nearest and possibly next nearest
neighbours contributions is in general sufficient to describe a system.
Angular forces are in addition needed to describe rigid lattices like those of
semiconductors.
For a periodic structure the system of equations separates into subsets of
3s equations, with s the number of unit cells, using Blochs theorem which
allows for plane wave solutions with frequency and wavevector q
)) ( ) ( ( n r q t q i
r r r

=

,
2
) (
) , ; , (
) ( ) (
m
m u
u u
m n
n u n M
& &
)) ( ) ( (
, 0
0
) (
n r q t q i
e u n u
r r r

=


which are the solutions for phonons of the 3D solid.
At the surface the 3D symmetry is broken and we have to consider the
coordinates in the surface plane separately from the vertical direction.
It is useful to introduce mass normalised amplitudes . Denoting the unit
cells by l
||
and l
z
and the positions of atoms within the unit cell with and
the spatial directions with ,, we get:
) ( ) ( ) (
|| ||

z z z
l l u l M l l =
looking for solutions with a time dependence of the form e
-it
we get from the equation of motion
) ; (
' ' '

l l l l
0 ) ( ) ; ( ) (
' ' '
||
' ' '
|| || ||
2
' ' '
||
=




z
l l
z z z
l l l l l l D l l
z
With D

the dynamical matrix of the system given by:

) ( ) (
) ; (
) ; (
' '
' ' '
|| ||
' ' '
|| ||

z z
z z
z z
l M l M
l l l l
l l l l D

=
D

is symmetric with respect to the interchange of primed and of non primed

symbols and depends only on l
//
-l
//
because of translational symmetry in the
surface plane. Given the eigenvectors e

(q
//
;l
z
) we can rewrite:
) ; (
|| ||
|| 0 ||
) ; ( ) (



z
l q r q i
z z
e l q e l l
r r r
r

=
and inserting into the equation of motion we obtain the secular equation
in which
is the Fourier transformed dynamical matrix
0 ) ' ' ; ( ) ' ' ; ; ; ( ) ; ( ) (
||
) (
' '
|| || ||
) (
||
2
=




z
s
l
z z z
s
s
l q e l q l q d l q e q
z
r r r
) ' ' ; ; (
||

z z
l l q d
Whose solutions, the eigenfrequencies, are given by the zeros of the
determinant
) ' ' ' ( ) ( (
|| ||
'
||
|| 0 || 0 ||
||
) ' ' , ' ; , ( ) ' ' ; ; (



z z
l l r l l r q i
z z
l
z z
e l l l l D l l q d
r r r

=
( ) 0 ) ' ' ; ; ( ) ( det
|| ||
2
=
z z s
l l q d q
r
Note that the solutions are for
2
not for
Projection of the 3D Brillouin Zone on the surface
3D fcc Wigner Seitz cell
2D fcc (111) Brillouin Zone
Projection to 2 D
Modes of an infinite and of a semi-infinite one dimensional
diatomic chain
Vibrational Vibrational Vibrational Vibrational dynamics dynamics dynamics dynamics
k force constant between
nearest neighbors
Equations of motion:
( ) ( ) ( )
( ) ( ) ( )

= =
= =
+ +

(1)
1 n
(1)
n
(2)
n
(1)
1 n
(2)
n
(2)
n
(1)
n
(2)
n
(2)
1 n
(2)
n
(1)
n
(2)
1 n
(1)
n
(1)
n
(2)
n
(1)
n
s s - s 2 k s s k s s k s m
s s - s 2 k s s k s s k s M
& &
& &
We look for a plane wave solution
with wavevector q

=
=
+

t) )
4
1
i(qa(n
2
(2)
n
t) )
4
1
i(qa(n
1
(1)
n
e c s
e c M s
m
( ) ( ) ( )

= =

(2) (2) (1) (2) (1) (1) (2) (1)
s s - s 2 k s s k s s k s M
& &
( )
( )

= +
|
|

\
|
+
=
|
|

\
|
+ +

0 c 2k m c e e
M
m
k
0 c e e
m
M
k c 2k M
2
2
1
2
iqa
2
iqa -
2
2
iqa
2
iqa
1
2
2
qa
cos
( ) ( ) ( )
( ) ( ) ( )

= =
= =
+ +

(1)
1 n
(1)
n
(2)
n
(1)
1 n
(2)
n
(2)
n
(1)
n
(2)
n
1 n n n 1 n n n n n
s s - s 2 k s s k s s k s m
s s - s 2 k s s k s s k s M
& &
& &
|
|
|
|

\
|
+
+
2
2
m 2k
2
qa
cos
M
m
2k
2
qa
cos
m
M
2k M 2k
DYNAMICAL MATRIX DYNAMICAL MATRIX DYNAMICAL MATRIX DYNAMICAL MATRIX
Solutions are given by the zeros
of the determinant
i.e.:
( )( ) 0
2
qa
cos 2k m 2k M 2k
2
2 2
=
|

\
|
+ +
( ) ( ) ( ) ( )
(

+ + =

qa cos 1 2Mm m M m M
mM
k

2
2
Bulk modes
modes Optical (q)
modes Acoustical (q)
+

q
LA
TA
Three polarizations
TO
Transverse optical
modes (TO)
generate a dipole
moment (centroid of
diatomic
chain
Longitudinal acoustical
mode at q=0
longitudinal optical
mode at q=0
Transverse
optical
mode at q=0
Eigenvectors
moment (centroid of
positive charge
moves with respect to
the centroid of the
negative charges).
Can be excited
optically by absorbing
Infrared Radiation or
by electron energy
loss in dipole
scattering.
Equilibrium
configuration
IR inactive
phonon
IR active
phonon
mode at q=0
Surface modes Surface modes Surface modes Surface modes
I R
iq q q
~
+ =
REAL REAL REAL REAL
a) a)sinh(q isin(q a) a)cosh(q cos(q a) q
~
cos(
I R I R
=
{ } 0 a) a)sinh(q sin(q 0 a) q
~
cos( Im = = =
We repeat the calculation with
( ) ( ) ( ) ( )
(

+ + =

a q
~
cos 1 2Mm m M m M
mM
k

2
2
{ } 0 a) a)sinh(q sin(q 0 a) q
~
cos( Im
I R
= = =
0 q
I
= VOLUME BRANCHES VOLUME BRANCHES VOLUME BRANCHES VOLUME BRANCHES
K 2 1, 0, n with
n a q e 0 q
R I
=
=
SURFACE SOLUTIONS SURFACE SOLUTIONS SURFACE SOLUTIONS SURFACE SOLUTIONS
( ) ( )
( ) ( ) z isinh iz sin
z cosh iz cos
=
=
( )
t) r q i( z q
q q q
// //
//
e e e

A r s

=
r r
r
r
( ) a) cosh(q 1) ( a) cosh(q n cos a) q
~
cos(
I
n
I
= =
We thus get:
in the first Brillouin zone
( )
( ) ( ) ( ) ( )
BULK s
0
I
2
2
I I R

a q cosh 1 2Mm m M m M
mM
k

a q 0 a) cosh(q - 1 0 n 0 q
>
(
(

+ + =
< = =
>

4 4 4 4 4 3 4 4 4 4 4 2 1
in the first Brillouin zone
Surface modes can exist only above
the bulk highest frequency
for n=1 the solutions are located at the 3D zone boundary
MAX
I
2 2
I
R
q
2Mm
m M
arccosh
a
1
q

a

q
=
|
|

\
|
+
<
=
Solutions exist only inside the band-gap i.e. between upper and lower bulk
bands
( ) ( ) 0 0 q
2k m) 2f(M
0 q
I I
= = =
+
= =
+

( ) ( ) 0 0 q
Mm
0 q
I I
= = = = =
+

( )
( )
( )

k
q q
M
2k
0 q

m
2k
0 q
MAX
I I
I
I
= =
= =
= =

+
q
I II I
q
R RR R
( ) )
1
M
1
k( q q
max I I
m
+ = = Surface bands
Boundary conditions:
)
~
( (i)
n
s
t z q i
i
i
n
e C

)
4
1
- a(n =
i
n
z
)
4
1
a(n + =
i
n
z
with for atom (1)=(i) and
for atom (2)=(i)
Given
I I R
iq
a

iq q q
~
+ = + = we obtain solutions of the form (q
I
>0)
q
I II I
q
R RR R
t i z q
e e
i
n I

~
(i)
n
s
a
whose vibrational amplitude
decays towards the bulk
For a three dimensional crystal with surfaces
there are solutions of the form
t i
r q i
z q
q q q
e e e Ae

=
) (
~
, , q
|| ||
|| ||
s
With an additional index in case there is more than one atom
per unit cell.
A surface phonon is thus characterized by its frequency, its
wavevector and by the way it decays towards the bulk. wavevector and by the way it decays towards the bulk.
These quantities are related by the boundary condition that no
forces act on the topmost layer of atoms.
We obtain a set of:
) , (
||
q q
One mode, the Rayleigh wave, characterized by an acoustic
dispersion, survives up to the continuum limit.
In earth quakes it is responsible for the largest damages, at
surfaces it influences the rate of catalytic reactions.
Surface Modes

M K
Penetration of surface modes into the bulk
The character of the surface modes may change over the 2D zone
Case of fcc (100)
Along -X S
1
is SH, along -M it is sagittal
Elastic continuum limit
The Rayleigh wave persists
in the elastic continuum limit.
Its velocity is smaller than
those of all bulk waves
moving in the same
direction.
The motion takes place in
the sagittal plane, i.e. The
atoms move both vertical
Rayleigh wave
atoms move both vertical
and parallel to the surface.
fcc (001) anisotropy of the Rayleigh wave and pseudo wave
Pseudo surface wave
decoupled by symmetry
from the bulk modes
Application: high frequency filters Application: high frequency filters Application: high frequency filters Application: high frequency filters
Transmitter: The high voltage
electric field induces strain in the
piezoelectric crystal with q=2/.
When such frequency coincides
with the dispersion of the Rayleigh
wave =
R
(q)=v
R
q
Rayleigh waves are excited in a
narrow spectral range

=
jk
jk ijk i
d P
q
q
ijk ij
E d

=
Receiver: An electric polarization
P is induced by the strain field
narrow spectral range
Effect of surface stress on the Rayleigh wave
In points of high symmetry such as the point of the 2D BZ of
fcc(100) the frequency of the Rayleigh wave can be calculated
easily without solving the secular equation and reads:
12
2
12
2
2 45 cos 4 ) (
1
k k M M
S
= =
) ( 2 45 cos ) ( 4 ) (
12
2
12
2
2
b b S
k k k k M M + = + =
1
st
layer mode
2
nd
layer mode
M
k
12
force constant
between first and
second layer
k
b
bulk force constant
Effect of surface stress on the Rayleigh wave
In points of high symmetry such as the point of the 2D BZ of
fcc(100) the frequency of the Rayleigh wave can be calculated
easily without solving the secular equation and reads:
12
2
12
2
2 45 cos 4 ) (
1
k k M M
S
= =
) ( 2 45 cos ) ( 4 ) (
12
2
12
2
2
b b S
k k k k M M + = + =
b
k
M M
4
) (
2
=

while the uppermost bulk frequency is

1
st
layer mode
2
nd
layer mode
M
b
b
k
M M
4
2
) (
=

while the uppermost bulk frequency is

In presence of a stress field the force
) (
11
'
11
s
a =
acts on the surface atoms changing the equation of motion.
For the Nearest Neighbour central force model we obtain:
a k M
S
/ ' 2 ) M (
12
2
1
+ =
Clean metallic surfaces have a tensile stress which may stiffen the
Rayleigh wave
Rayleigh wave anomaly
on metal surfaces
The frequency of the Rayleigh
wave at the 2D Zone Border
is higher than expected for
most metal surfaces.
The effect may be either due
to an increase of the force
constant between first and
second layer or to surface
Tensile (compressive)
stress at metal surfaces
causes a stiffening
(softening) of the Rayleigh
wave frequency
second layer or to surface
stress. The latter explanation
is the currently accepted one.
tensile
no stress
compressive
Slab method
Green function method
Theoretical methods of Surface Dynamics
Green function method
Molecular dynamics
Slab method
Analogous to the electronic state calculations. The
equation of motion is solved for a slab and one gets
a spaghetti diagram
Green Function method
The surface is considered
as a perturbation affecting
the bulk phonon spectrum.
The secular equation is a
differential equation and it
is solved mathematically
by the Green function by the Green function
method. The surface term
is introduced as a
perturbation of the bulk
solution.
Molecular dynamics
The molecular dynamics method consists in
calculating the atomic positions vs time.
The Fourier transform vs space gives the k
vector of the phonons, while vs time it allows
to recover the phonon frequency spectrum to recover the phonon frequency spectrum
Ab initio methods Ab initio methods Ab initio methods Ab initio methods
By virtue of the Born Oppenheimer approximation, phonons are a
property of the electronic ground state. At the high symmetry
points of the 3D Brillouin Zone the eigenvectors correspond to
particularly simple motions (e.g. at fcc X to the sliding of the
(100) planes against each other) and the potential energy
associated to such motion can be calculated relatively easily by
doubling of the unit cell (frozen phonon method). At the surface
things are not as easy, but also in that case one can calculate the
energy of the distorted lattice and then compute the second
derivative of the E(x) curve.
Adsorbate modes Adsorbate modes Adsorbate modes Adsorbate modes
Dynamics in presence of an adsorbed layer
Adsorbate modes contain information on the
lateral interaction between the adsorbates
Phonon anomalies
Soft phonons induced by adsorbates
which modify the surface stress
Soft phonons induced by electron
phonon interaction (Kohn anomaly)
Sulfur induces a softening of the RW because of loading
while oxygen induces a much larger effect because of the
compressive stress it introduces into the surface layer
The Rayleigh wave goes soft for
2 / ' '
12
) (
11

s
corresponding to compressive stress (soft phonon)
a M
S
/ ' ' ' 2 ) M (
12
2
1
+ =
Before this happens the A
2
mode at X goes however soft, too, for:
4 / ' '
12
) (
11

s
12 11
so that the surface reconstructs with p4g symmetry.
This situation happens e.g. for the c(2x2) overlayers of C and N on Ni(100).
For O/Ni(100), on the contrary, the stress is large but still insufficient to
cause the freezing in of the A
2
mode.
Effect of surface stress Effect of surface stress Effect of surface stress Effect of surface stress
Phase transition and soft modes
Reconstruction of W(001)
Atoms are pairing in rows
Artificially stressed surfaces
Kohn anomaly Kohn anomaly Kohn anomaly Kohn anomaly
The electron phonon interaction causes a rigid shift of the Fermi sphere
and a failure of the Born oppenheimer approximation since the
electrons do not follow any more the ionic motion adiabatically.
Fermi sphere
Kohn anomaly
The Kohn anomaly occurs e.g. for bulk Pt.
The phenomenon is expected to be particularly strong for materials which
present parallel planes in the Fermi surface, the so called surface nesting.
direct lattice
reciprocal lattice
For 2D materials the Kohn anomaly is observed only for
W(110)-H and Mo(110)-H. In this case the Fermi surface
reduces to a Fermi line.
The upper branch is of phononic character and is observed
both in HREELS and in inelastic He atom scattering (IHAS).
The lower branch is due to (e-h) pairs and is excited only by
.
anomaly
line
Filled symbols HREELS: phonon only
Open symbols IHAS: phonon and e-h
pairs
The anomaly is observed all along
the line running parallel to -N.
The effect is thus due to one-
dimensional nesting
2q
F
Explanation of the Kohn anomaly.
Since the effect is observed only in presence of the (1x1) H phase, nesting
is due to an adsorbate induced electronic state