Answers to Exercises

9
Answers to Exercises from Chapter 1.
Surface and Adsorbate Structure
1.1

a(a) Determine the surface atom density of Ag(221).

Ag packs as an fcc crystal with a lattice parameter of 0.408 nm. Therefore according to
Eq. (1.1.1)
0 =

4
2(0.408

107 cm)2 (22

+ 22 + 12 )1/2

= 4.00 1014 cm2

(b) For the basal (cleavage) plane of graphite, determine the unit cell length, a, the included angle
between sides of the unit cell, , and the density of surface C atoms, 0 , given that the CC near A representation of the graphite surface is given in Fig. 1.20.
est neighbour distance is 1.415 A.
First make a few geometrical identications

Figure Exercise 1.1 Graphite basal plane.

1 = 2 = 3 = ;

3 = 360 = 120

= 90, + = = 30
There are two ways to calculate 0 .

+ 2 = = 60

Surface Science: Foundations of Catalysis and Nanoscience, Third Edition. Kurt W. Kolasinski.
c 2012 John Wiley & Sons, Ltd. Published 2012 by John Wiley & Sons, Ltd.


416

Surface Science: Foundations of Catalysis and Nanoscience

(i) Calculate the area of the hexagon. Note that each C atom is shared between three equivalent
hexagons and therefore contributes 1/3 of an atom to any given hexagon. 6(1/3) = 2 atoms per
hexagon. Dividing 2 atoms by the area of the hexagon will yield the density of surface atoms.
Divide the hexagon into two equivalent triangles with side lengths s1 , s1 and s2 and one
rectangle of side lengths s1 and s2 . The area of the hexagon is the sum of the areas of the two
triangles and the rectangle.
s
sin
s1

= 2 s2 = s1
= 2.451 A
sin
sin
sin


sin
s1 s2 sin
2
+ s1 s2 = s1 s2 (sin + 1) = s12
(sin + 1) = 5.202 A
Ahex = 2
2
sin
0 =

2
=
Ahex

5.202 A

2


1 cm

108 A

15
2
2 = 3.845 10 cm

a = s2 = 2.451 A.
(ii) Calculate the area of the unit cell. Note that there are two atoms per unit cell (the one in the
center of the cell and the one derived from the four corner atoms, which are shared between
four unit cells.

Aunit cell = a 2 sin = s22 sin = 5.202 A

0 =

1.2

2
Aunit cell

2
= 3.845 1015 cm2
2

5.202 A (1 cm/108 A)

The answers are, as expected, equal.

The Pt(111) surface has a surface atom density of 0 = 1.503 1015 cm2 . (a) Calculate the diameter of a Pt atom. (b) Calculate the atom density of the Pt(100) surface.

(a)

(b)

Figure Exercise 1.2 Unit cells of (111) and (100) surface lattices.

There is one atom in the (111) unit cell. The side of the unit cell is equal to the diameter of the Pt
atom. The area of a parallelogram is equal to the length of the base times the height.
Aunit cell = ah.
The length of the base, a, is also equal to the diameter of a Pt atom dPt . The line segment that
denes the height bisects the base into two equal portions of length a/2 to form a right triangle.
Thus the height is a 2 = h 2 + (a/2)2

3
a
h=
2

Answers to Exercises from Chapter 1. Surface and Adsorbate Structure

and the area of the unit cell is

Aunit cell

417

3 2
3 2
a =
d
=
2
2 Pt

The areal density is then

0 (111) =

1
Aunit

=
cell

3 2
2 dPt

From which the Pt atom diameter can be calculated.



2
2
dPt =
= 2.772 108 cm.
=
1.732(1.503 1015 )
30
(a) In the square lattice of the Pt(100) surface, there is one atom per unit cell and the area of the
unit cell is simple a 2 .
0 (100) =
1.3

1
Aunit

=
cell

1
1
=
= 1.302 1015 cm2
2
(2.772 108 cm)2
dPt

a(a) Derive a general expression for the step density, step , of an fcc crystal with single-atom-height
steps induced by a miscut angle from the ideal surface plane.
(b) Make a plot of step density versus miscut angle for an fcc crystal.

(a)

Figure Exercise 1.3(a) Side view of a stepped surface.

(a) Steps occur each time an atom is intersected by the macroscopic surface plane. In other words,
you cannot have a fraction of an atom. A step occurs each time the side b of the triangle is
equal to the diameter of a metal atom. The terrace width is the length a.
tan =

b
a
a=
= nterrace dM ,
b
tan

where nterrace is the number of terrace atoms and dM is the metal atom diameter. There is one
step for every nterrace surface atoms; hence the step density is
step =

1
= tan
nterrace

(b) As shown in the gure below, a plot of tan is essentially linear at the small angles of interest.

418

Surface Science: Foundations of Catalysis and Nanoscience

(b)

Figure Exercise 1.3(b) Step density as a function of miscut angle.

1.4

1.5

Discuss why surface reconstructions occur. On what types of surfaces are reconstructions most
likely to occur and where are they least likely to occur?
A surface created with the structure of the terminated bulk lattice is not the conguration with the
lowest total surface energy. Generally, on metal surfaces simple relaxations (small changes in bond
lengths and angles) are sufcient to obtain a stable surface. On covalently bonded surfaces, such as
those of semiconductors and oxides, larger relaxations occur which result in a new periodicity of
the surface atoms with respect to the bulk-truncated structure. The formation of a structure with a
new periodicity is a reconstruction.
The Fermi energies of Cs, Ag and Al are 1.59, 5.49 and 11.7 eV, respectively. Calculate the density
of the Fermi electron gas in each of these metals as well as the Fermi temperature. Calculate the
difference between the chemical potential and the Fermi energy for each of these metals at their
respective melting points.
From Eq. (1.3.8)
2
EF =
(3 2 )2/3
2me
and Eq. (1.3.7)


(T ) EF

2
1
12

with the Fermi temperature

TF =

EF
.
kB

kB T
EF

2 

Answers to Exercises from Chapter 1. Surface and Adsorbate Structure

Therefore,
1
=
3 2


and
(T ) EF EF

2
1
12

kB T
EF

2me
2

3/2

419

3/2

EF

2 


EF = EF

2 kB2
12

T
EF

2 
.

This can be used to complete the following table.

EF /ev
EF /1019 J
TF /K
Tf /K
/1028 m3
EF /eV

1.6

Cs

Ag

Al

1.59
2.547
18 460
300.55
0.922
3.46 104

5.49
8.796
63 740
1235.08
5.92
1.70 103

11.7
18.75
135 900
933.52
18.4
4.55 104

Note that the shift in the chemical potential is negative and very small.
A clean Ag(111) surface has a work function of 4.7 eV. As a submonolayer coverage of Ba is dosed
onto the surface, the work function drops and reaches a minimum of 2.35 eV. Calculate the surface
potential associated with the clean and Ba covered surfaces and explain the effect of Ba adsorption
on the work function of Ag(111).
The Fermi energy of Ag is 5.49 eV. Thus, by rearranging Eq. (1.3.4) and with both
and EF
expressed in eV, we nd that the surface potential is



+ EF
=
.
e
Hence for the clean and Ba covered surfaces


4.7 eV + 5.49 eV
= 10.19 V.
{Ag(111)} =
e


2.35 eV + 5.49 eV
{Ba/Ag(111)} =
= 7.84 V.
e

1.7

Ba adsorption lowers the work function of the surface by reducing the magnitude of the surface
dipole. Ba is more electropositive than Ag, i.e. it has a lower work function than Ag; therefore it
donates charge to the Ag substrate.
The work function of clean Al(111) is 4.24 eV [1] (a free electron sp metal), clean Ag(111) is
4.7 eV (a coinage metal), and for bulk polycrystalline Cs is 2.14 eV (an alkali metal). Use the value
of the Fermi energy given in Exercise 1.5 to calculate the surface potential for these three different
types of metals.
From Eq. (1.3.4), the surface potential is



+ EF
.
=
e

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1.8

Surface Science: Foundations of Catalysis and Nanoscience

The Fermi energies of Al, Ag and Cs are 11.7, 5.49 and 1.59 eV, respectively. Hence the surface
potentials are 15.94, 10.19 and 3.78 V, respectively. Note that the surface potential is over 4
times greater on Al(111) as compared to Cs and over 2.5 higher on Ag(111) than on Cs.
The magnitude of an electric dipole is
= 2qR

(1.8.1)

for a charges +q and q separated by a distance 2R. The work function change 
expressed in V
associated with adsorption of a species with charge q, located a distance R from the surface (hence
its image charge is at a distance 2R from the adsorbate and R below the plane of the surface) at
a coverage is given by the Helmholtz equation

= /20 = qR/0 ,

(1.8.2)

when the dipole moment and coverage are expressed in SI units.

Calculate the work function changes expected for 0.1 ML of either peroxo (O2 2 ) or superoxo
The measured work function
(O2 ) species bound on Pd(111) given that their bond distance is 2 A.
change is only on the order of 1 eV. Explain the difference between your estimates and the measured
value.
From Table 1.1, we nd 0 = 1.53 1019 m2 for Pd(111). For the superoxo species, we substitute q = 1.602 1019 C and R = 2 1010 m. Hence

=

1.9

1.10

0.1(1.53 1019 m2 )(1.602 1019 C)(2 1010 m)

8.85 1012 C2 J1 m1

= 5.74 JC1 = 5.74 V,

Since the charge q is twice as large on the peroxo species, the predicted work function change is

= 11.5 V.
The differences can be ascribed to polarization effects within the adsorbed layer as well as to
screening effects, and the breakdown in assuming that the transferred charged is localized as a point
charge rather than a charge distribution about the adsorbed molecule [2].
The work function of Pt(111) is 5.93 eV. A Ru lm has a work function of 4.71 eV. If Ru islands
are deposited on a Pt(111) surface, in which direction does electron transfer occur?
Charge transfer occurs from the low work function metal to the high work function metal; thus
from Ru to Pt. Consider this: when not in contact, the vacuum levels are at the same position. The
Fermi levels are at two different energies, with the Pt Fermi level signicantly below that of the
Ru in order to achieve the larger work function of Pt. When the two metals are brought in contact,
the Fermi levels must align, and the vacuum levels will be realigned by the change in the surface
potential. Electron transfer must occur to achieve this realignment. Since electron ow from high
energy to low, electrons will ow out of the Ru toward the Pt.
Redraw Fig. 1.17 for a p-type semiconductor.
The energy difference in the bulk between EC , EF and EV is a constant. The energy difference
between EC and EV is constant throughout the semiconductor. In n-type material, EF is just below
EC whereas in p-type material, EF is just above EV . At equilibrium the Fermi energies of the metal
and semiconductor must be equal. In order to accommodate these conditions, the position of EC
and EV (and Evac ) relative to EF must change at the surface and in the space charge region. The
sense of the change is opposite for n-type and p-type materials.

Answers to Exercises from Chapter 1. Surface and Adsorbate Structure

421

Figure Exercise 1.10 Band bending for a p-type semiconductor.

1.11

Given that the partition function, q, is dened by a summation over all states according to
q=

exp(Ei /kB T )

(1.8.3)

i =1

where Ei is the energy of the i th state. Use Eq. (1.4.4) to show that the mean vibrational energy of
a solid at equilibrium is given by Eq. (1.4.6). Hint: The mean energy is given by
E = kB T 2

(ln q)
T

From Eq. (1.4.4), the energy of the n th state is given by



E (k, p) = n(k, p) + 12 k (p)

(1.8.4)

422

Surface Science: Foundations of Catalysis and Nanoscience

The summation in the partition function runs over all quantum states. Since the quantum number
of the ground state of our oscillator is for n(k, p) = 0, the summation is given by


[n(k, p) + 12 ]k (p)
exp
q=
.
kB T
n=0

To simplify, we dene a vibrational quantum given by

k
(p) = vib = k (p), introduce =
vib

1
,
kB T

and drop the branch label, therefore


q = exp

vib
2

exp(nvib ).

n=0

Note, however, that the k /2 term in Eq. (1.4.4), which leads to the exp(vib /2) term above, is
simply related to the zero point energy, which leads to a constant k /2 that we can add into the
mean energy at the end. We are left to evaluate
q=

exp(nvib ).

n=0

This summation represents a geometric progression, that is, an innite series

s = 1 + x + x2 . . .
which, because x 2 < 1, rearranges to
s=

1
, where x = exp(vib )
1x

In our case
q=

1
1
=
.
1x
1 exp(vib )

We now take the derivative of the natural log of the partition function with respect to T , or rather,
we must convert to a derivative with respect to .
ln q
ln q
ln q
ln q
=
= kB
= kB T 2

(1/kB T )
(1/T )
T
Thus
E = kB T 2



ln q

1
exp(vib )
ln q
=
=
ln
= vib
.
T

1 exp(vib )
1 exp(vib )

We need to add in the zero-point contribution and, upon rearranging




exp(vib ) exp(vib )

vib
E = vib + vib
= vib +
2
1 exp(vib ) exp(vib )
2
exp(vib ) 1
as was meant to be shown.

Answers to Exercises from Chapter 1. Surface and Adsorbate Structure

1.12

423

The Debye temperature,

D = D /kB ,

(1.8.5)

is more commonly tabulated and determined than is the Debye frequency because of its relationship
to the thermodynamic properties of solids.
(a) Calculate the Debye frequencies of the elemental solids listed below in Hz, meV and cm1 .
(b) Calculate the mean phonon occupation number at the Debye frequency and room temperature
for each of these materials at 100, 300 and 1000 K.

D (K)

Ag

Au

diamond

graphite

Pt

Si

225

165

2230

760

240

645

400

(a) Rearranging Eq. (1.8.5) and converting appropriately, we have

 
kB
D =
D = (1.309216 1011 s1 K)D

D =
For meV D =

D
(c in cm s1 then D in cm1 )
2 c

D
8.065 cm1 meV1
n(k, p) n(k (p), T ) =

D (K)
D (/1013 Hz)
D (cm1 )
meV
n(D , 100 K
n(D , 300 K
n(D , 1000 K
1.13

1
exp(k (p)/kB T ) 1

Ag

Au

diamond

graphite

Pt

Si

225
2.94
156
19.4
0.118
0.895
3.96

165
2.16
115
14.2
0.238
1.36
5.57

2230
29.2
1549
192
2 107
6 104
0.12

760
9.95
528
65.5
5 104
0.0862
0.879

240
3.14
167
20.7
0.0998
0.821
3.69

645
8.44
448
55.5
1.6 103
0.132
1.1

400
5.24
278
34.4
0.0187
0.358
2.03

The Debye model can be used to calculate the mean square displacement of an oscillator in a solid.
In the high-temperature limit this is given by
u 2 =

3NA 2 T
MkB D2

(1.8.6)

(a) Compare the root-mean-square displacements of Pt at 300 K to that at its melting point (2045 K).
What is the fractional displacement of the metal atoms relative to the interatomic distance at
the melting temperature?

424

Surface Science: Foundations of Catalysis and Nanoscience

(b) Compare this to the root-mean-square displacement of the C atoms at the surface of diamond
at the same two temperatures.
According to the Debye model the root-mean-square displacement of Pt is given by



3NA 2T
T
T
1/2 1/2
2 1/2
11
1/2 1/2
kg K
= 3.815 10
m kg K
= 0.3815 A
u =
MkB D2
M D2
M D2
with M = 0.19508 kg mol1 and D = 240 K.
and u 2 1/2 |2045
Thus u 2 1/2 |300 K = 0.0623 A

= 0.163 A.

For the fractional displacement we need to calculate theequilibrium PtPt distance. Since Pt is an
fccmetal, the nearest neighbour distance is given by a/ 2 (where a is the lattice constant) = 3.92
2 = 2.77 A.
Therefore,
A/
u 2 1/2 |300 K
u 2 1/2 |2045 K
= 0.0225 and
= 0.0588.

2.77A
2.77 A
(a) For diamond M = 0.0120 kg mol1 and D = 2230 K.
and u 2 1/2 |2045 K = 0.0706 A.

Thus u 2 1/2 |300 K = 0.0271 A

1.14

The absolute motion of a C(diamond) atom at these temperatures corresponds to only about 43%
of that of a Pt atom.
The surface Debye temperature of Pt(100) is 110 K. Take the denition of melting to be the point
at which the fractional displacement relative to the lattice constant is equal to 8.3% (Lindemann
criterion). What is the surface melting temperature of Pt(100)? What is the implication of a surface
that melts at a lower temperature than the bulk?
Solving the root mean square displacement equation, Eq. (1.8.6), for T yields
Tf = M D2 (0.083x /c)2

1.15

kg1/2 K1/2 . The surface

where x = 2a is the nearest neighbour distance and c = 0.3815 A
Tf (surface) = 857
melting temperature is found by substituting s = 110 K for D and x = 2.77 A.
K, signicantly below the bulk melting point of 2045 K.
A liquid layer covers the bulk solid. The layer grows in thickness as each successively deeper
solid layer becomes the surface layer of the solid. Thus melting starts at the surface and proceeds
back into the bulk.
The bulk terminated Si(100)(1 1) surface has two dangling bonds per surface atom and is,
therefore, unstable toward reconstruction. Approximate the dangling bonds as effectively being halflled sp 3 orbitals. The driving force of reconstruction is the removal of dangling bonds. (a) The
stable room temperature surface reconstructs into a (2 1) unit cell in which the surface atoms
move closer to each other in one direction but the distance is not changed in the perpendicular
direction. Discuss how the loss of one dangling bond on each Si atom leads to the formation
of a (2 1) unit cell. Hint: The nearest neighbour surface Si atoms are called dimers. (b) This
leaves one dangling bond per surface atom. Describe the nature of the interaction of these dangling

Answers to Exercises from Chapter 1. Surface and Adsorbate Structure

1.16

1.17

1.18

425

bonds that leads to (i) symmetric dimers and (ii) tilted dimers. (c) Predict the effect of hydrogen
adsorption on the symmetry of these two types of dimers. Hint: Consider rst the types of bonds that
sp 3 orbitals can make. Second, two equivalent dangling bonds represent two degenerate electronic
states.
There are two ways in which the sp 3 like dangling bond orbitals can interact. (a) bond formation. This leads to symmetric dimers as one would expect based on the symmetry of the bonding
interaction and the equivalence of the two bonding orbitals. (b) The two dangling bonds represent
two degenerate half-lled electronic states when they are in a symmetric conguration. Such a system is unstable with respect to a Jahn-Teller distortion unless some other interaction overrides the
Jahn-Teller effect. Therefore, the system will spontaneously break symmetry by tilting the dimer.
This leads to a splitting of the electronic states into two states, with a higher population of electrons
in the lower energy state than in the higher energy state.
H atom adsorption breaks the bond and negates the Jahn-Teller effect. Thus, regardless of
which interaction was rst present, the structure of the dimer with one H atom on it will be the
same in either case. It is unclear whether this should be symmetric or not based on simple arguments
but it will be less symmetric than a dimer with two H atoms adsorbed and less tilted than a dimer
with no H atoms adsorbed. A dimer with two adsorbed H atoms will be symmetric.
Describe the features a, b, c, and d in Fig. 1.19.
(a) is an occupied surface resonance. It is a resonance since it falls in an allowed part of the
projected bulk band structure, i.e. it overlaps bulk bands.
(b) is an occupied surface state. It is a surface state because it appears in part of the band gap (a
region where bulk states are forbidden). Both a and b are occupied because they are located
below the Fermi energy, EF .
(c) is a normally unoccupied surface state.
(d) is a normally unoccupied surface resonance. Both c and d are normally unoccupied because
they lie above EF .
What is the signicance of a band gap? (b) What differentiates a partial band gap from a full band gap?
(a) A band gap is a region of k space in which no bulk bands exist. Only defect states or surface
states can have the combination of energy and momentum that lies in a band gap. Any state
that lies in a band gap will be weakly coupled to bulk states and the farther away it is from a
band edge, the more weakly it will be coupled (all other things such as symmetry being equal).
The presence and size of a band gap also determines whether a material is a metal, semimetal,
semiconductor or insulator.
(b) A partial band gap is a small region of k space in which states of a given energy are not allowed.
A full band gap exists in a certain energy range for all values of crystal momentum.
What are Eg , EF , EC , EV and Evac as shown, for instance, in Fig. 1.19?
Eg is the magnitude of the band gap. A band gap can be either direct (the minimum vertical energy
difference in a diagram such as Fig. 1.19) or indirect (the minimum energy difference, which occurs
between points with different values of k).
EF is the Fermi energy. It is the highest allowed energy for electrons at 0 K. However, in a
perfect intrinsic (undoped) semiconductor, there are no states at EF because it lies midway in the
band gap.
EC is the conduction band minimum, the lowest energy point in the conduction band.
EV is the valence band maximum, the highest energy point in the valence band.

426

Surface Science: Foundations of Catalysis and Nanoscience

Evac is the vacuum energy, above which electrons are no longer bound to the solid. The difference
between Evac and EC is the electron afnity. The difference between Evac and EF is the work function.

References
[1] A. Hohlfeld, M. Sunjic, K. Horn, J. Vac. Sci. Technol. A, 5 (1987) 679.
[2] L. Schmidt, R. Gomer, J. Chem. Phys., 42 (1965) 3573.