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Geometric and Electronic
Properties of
Graphene-Related Systems
Ngoc Thanh Thuy Tran, Shih-Yang Lin, Chiun-Yan Lin, Ming-Fa Lin

Geometric and Electronic

Properties of
Graphene-Related Systems

Chemical Bonding Schemes

CRC Press
Taylor & Francis Group
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Contents

List of Figures vii

List of Tables xv

Preface xvii

Authors xix

1 Introduction 1

2 Computational Methods 9

3 Few-Layer Graphenes 13
3.1 AAA Stacking . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2 ABA Stacking . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.3 ABC Stacking . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.4 AAB Stacking . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.5 The First-Principles Method and the Tight-Binding Model . . . 20
3.6 Comparisons and Experimental Measurements . . . . . . . . 24

4 Structure-Enriched Graphenes 31
4.1 Sliding Bilayer Graphene . . . . . . . . . . . . . . . . . . . . 32
4.2 Graphene Ripples . . . . . . . . . . . . . . . . . . . . . . . . 39

5 Graphene Oxides 49
5.1 Single-Side Adsorption . . . . . . . . . . . . . . . . . . . . . 51
5.2 Double-Side Adsorption . . . . . . . . . . . . . . . . . . . . . 60

6 Hydrogenated Graphenes 65
6.1 Single-Side Adsorption . . . . . . . . . . . . . . . . . . . . . 66
6.2 Double-Side Adsorption . . . . . . . . . . . . . . . . . . . . . 75

7 Halogenated Graphenes 83
7.1 Halogenation-Diversified Essential Properties . . . . . . . . . 84
7.2 Comparisons, Measurements and Applications . . . . . . . . 97

v
vi Contents

8 Alkali-Adsorbed Graphene-Related Systems 101

8.1 Alkali-Adsorbed Graphenes . . . . . . . . . . . . . . . . . . . 102
8.2 Alkali-Adsorbed Graphene Nanoribbons . . . . . . . . . . . . 111

9 Metallic Adatom-Doped Systems 119

9.1 Al-Adsorbed Graphenes . . . . . . . . . . . . . . . . . . . . . 120
9.2 Bi-Adatom Adsorption Configurations on SiC-Based
Graphene Surface . . . . . . . . . . . . . . . . . . . . . . . . 126

10 Concluding Remarks 133

Problems 141

Bibliography 143

Index 185
List of Figures

3.1 Geometric structures of tri-layer graphenes: (a) AAA stacking,

(b) ABA stacking, (c) ABC stacking, and (d) AAB stacking. A
unit cell covers six sublattices (A1 , B 1 , A2 , B 2 , A3 , B 3 ) in three
layers. Also shown are the significant intralayer and interlayer
hopping integrals. Blue and yellow balls, respectively, corre-
spond to A and B sublattices. . . . . . . . . . . . . . . . . . . 14
3.2 2D band structures for (a) AAA stacking, (b) ABA stacking,
(c) ABC stacking, and (d) AAB stacking. . . . . . . . . . . . 15
3.3 Low-lying 3D band structures around the k-point for (a) AAA
stacking, (b) ABA stacking, (c) ABC stacking, and (d) AAB
stacking. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.4 DOS for various tri-layer graphenes: (a) AAA stacking, (b)
ABA stacking, (c) ABC stacking, and (d) AAB stacking. . . . 17
3.5 Low-lying band structures of tri-layer (a) AAA, (b) ABA, (c)
ABC and (d) AAB stackings by the first-principles method
(solid curves) and the tight-binding model (dashed curves). . . 23
3.6 The schematic illustration of ARPES. . . . . . . . . . . . . . 26
3.7 Schematic diagram of STM. The tunneling current through tip
and sample controls the prober movement along the z-direction
from the feedback electronics and a high voltage amplifier.
Meanwhile, the voltage ramp is used for the x-y scanning. . . 27

4.1 (a) Geometric structure of bilayer graphene shifting along the

armchair and zigzag directions. (b) The shift-dependent total
ground state energy and interlayer distance (the dashed blue
and red dots), as measured from those of the AA stacking. . . 33
4.2 Low-energy band structures around the K point (heavy dashed
circles) for various stacking configurations along armchair (δa )
and zigzag (δz ) directions: (a) δa = 0, (b) δa = 1/8, (c) δa =
4/8, (d) δa = 1, (e) δa = 11/8, (f) δa = 12/8, (g) δz = 1/8, (h)
δz = 3/8. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.3 2D band structures along the high-symmetry points for various
stacking configurations: (a) δa = 0, (b) δa = 1/8, (c) δa = 4/8,
(d) δa = 1, (e) δa = 11/8, (f) δa = 12/8, (g) δz = 1/8, (h)
δz = 3/8. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

vii
viii List of Figures

4.4 DOS due to 2pz orbitals for various stacking configurations: (a)
δa = 0, (b) δa = 1/8, (c) δa = 4/8, (d) δa = 1, (e) δa = 11/8,
(f) δa = 12/8, (g) δz = 1/8, (h) δz = 3/8. . . . . . . . . . . . 38
4.5 The shift dependence of van Hove singularities at (a) low and
(b) middle energies. . . . . . . . . . . . . . . . . . . . . . . . 39
4.6 Geometric structures of (a) armchair ripple and nanotube,
(b) zigzag ripple and nanotube, (c) rippling period l and
the amplitude h, (d) rectangular Brillouin zone of graphene
ripple. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.7 (a) Energy bands of armchair ripples along the Γ Y direction
at distinct curvatures and periods. Band structures in energy-
wave-vector space for a Nλ = 6 armchair ripple at (b) Cr = 0.09
and (c) Cr = 0.53. Also shown in (a) is the dashed curve for a
(3, 3) armchair nanotube. . . . . . . . . . . . . . . . . . . . . 41
4.8 Energy bands of a Nλ = 5 zigzag ripple at various curvatures
along the (a–d) Γ X and (e) Γ Y directions. (f) and (g) Energy
bands for the critical curvature with periods of Nλ = 5 and
9. Band structures in energy-wave-vector space for a Nλ = 5
zigzag ripple at (h) Cr = 0.05 and (i) Cr = 0.27. Also shown in
(e) is the dashed curve for a (5, 0) zigzag nanotube. . . . . . . 43
4.9 The spatial charge distributions: (a) a planar graphene, (c) a
Nλ = 6 armchair ripple at Cr = 0.53 and (e) a Nλ = 5 zigzag
ripple at Cr = 0.27. (b), (d) and (f) are those for the charge
differences. The right-hand sides present four kinds of chemical
bondings between two carbons, and the similar distributions
for (3, 3) and (5, 0) nanotubes. . . . . . . . . . . . . . . . . . 45
4.10 Density of states: (a) armchair and (b) zigzag ripples with var-
ious curvatures and periods. The orbital-projected DOS for (c)
a Nλ = 6 armchair ripple at Cr = 0.53 and (d) a Nλ = 5 zigzag
ripple at Cr = 0.27. DOS of (3, 3) and (5, 0) nanotubes are
shown in (a) and (b), respectively. . . . . . . . . . . . . . . . 47

5.1 Geometric structures of GOs with various unit cells and concen-
trations: (a) zigzag O:C = 1:2 (Z), (b) armchair O:C = 3:6 (A),
(c) chiral O:C = 7:14 (C) (d) zigzag O:C = 1:8 (Z), (e) zigzag
O:C = 1:18 (Z), (f) armchair O:C = 1:24 (A), (g) zigzag O:C
= 1:50 (Z), and (h) zigzag O:C = 1:98 (Z). Various oxygen dis-
tributions are denoted by numbers, corresponding to different
concentrations listed in Table 5.1. . . . . . . . . . . . . . . . . 52
5.2 Band structures of GOs with various concentrations: (a) O:C
= 1:2 = 50% (Z), (b) O:C = 3:6 = 50% (A), (c) O:C = 7:4
= 50% (C), (d) O:C = 2:6 = 33.3% (A), (e) O:C = 2:8 =
25% (Z), (f) O:C = 4:18 = 22.2% (Z), (g) O:C = 1:24 = 5.6%
(Z), (h) O:C = 1:18 = 4.2% (A), (i) O:C = 3:98 = 3% (Z), and
List of Figures ix

(j) O:C = 1:98 = 1% (Z). Superscripts c and v correspond to the

conduction and valence bands, respectively. The red and blue
circles, respectively, correspond to the contributions of passi-
vated C atoms and O atoms, in which the dominance is pro-
portional to the radius of circle. Also shown in the inset of (a)
is the first Brillouin zone. . . . . . . . . . . . . . . . . . . . . 54
5.3 The band-decomposed charge density of (a) pristine graphene,
(b) 50% (Z), (c) 33.3% (A), (d) 4.2% (A), and (e) 1% (Z) O-
concentrations, in which the side views of π bondings are plot-
ted along the dashed orange line of the corresponding top view
one. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
5.4 The charge density (plotted in xz-plane) of (a) pristine
graphene, (b) 50% (Z), (c) 33.3% (A), and (d) double-side
25% (Z). The top view of charge density difference and its pro-
jections on xz- and yz-planes for (e) 50% (Z), (f) 33.3% (A),
and (g) double-side 25% (Z). The xy-plane projections are also
shown. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
5.5 Orbital-projected DOS of GOs with various O-concentrations:
(a) O:C = 1:2 = 50% (Z), (b) O:C = 3:6 = 50% (A), (c) O:C =
7:14 = 50% (C), (d) O:C = 2:6 = 33.3% (A), (e) O:C = 2:8 =
25% (Z), (f) O:C = 4:18 = 22.2% (Z), (g) O:C = 1:18 = 5.6%
(Z), (h) O:C = 1:24 = 4.2% (A), (i) O:C = 3:98 = 3% (Z), and
(j) O:C = 1:98 = 1% (Z). . . . . . . . . . . . . . . . . . . . . 59
5.6 Band structures of oxygen adsorbed few-layer graphenes:
(a) AA stacking, (b) AB stacking, (c) AAA stacking, and
(d) ABA stacking. . . . . . . . . . . . . . . . . . . . . . . . . 60
5.7 Band structures of double-side adsorbed GOs with the oxygen
concentration of (a) O:C = 4:8 = 50% (Z), (b) O:C = 2:6 =
33.3% (A), (c) O:C = 2:8 = 25% (Z), (d) O:C = 2:18 = 11.1%
(Z), (e) O:C = 2:50 = 4% (Z), (f) AA; O:C = 2:4 = 50% (Z)
stacking, (g) AB; O:C = 2:4 = 50% (Z) stacking, and (h) AAA;
O:C = 2:6 = 33.3% (Z) stacking. . . . . . . . . . . . . . . . . 62

6.1 Geometric structures of single-side hydrogenated graphene with

top view and side view: (a) H:C = 4:8 = 50% (Z), (b) H:C =
2:6 = 33.3% (A), (c) H:C = 2:8 = 25% (Z), (d) H:C = 1:6 =
16.7% (A), (e) H:C = 2:18 = 11.1% (Z), (f) H:C = 1:14 = 7.1%
(C), (g) H:C = 2:8 = 25% (Z), (h) H:C = 2:18 = 11.1% (Z),
(i) H:C = 2:24 = 8.3% (A), and (j) H:C = 2:32 = 6.3% (Z).
(g)–(j) do not have the spin configurations. . . . . . . . . . . 67
6.2 Band structures of single-side hydrogenated graphenes with
spin polarizations: (a) 50% (Z), (b) 33.3% (A), (c) 25%
(Z), (d) 16.7% (A), (e) 11.1% (Z), and (f) 7.1% (C) H-
concentrations. . . . . . . . . . . . . . . . . . . . . . . . . . . 69
x List of Figures

6.3 Band structures of single-side hydrogenated graphenes without

spin polarizations: (a) 25% (Z), (b) 11.1% (Z), (c) 8.3% (A),
and (d) 6.3% (Z) H-concentrations. . . . . . . . . . . . . . . . 70
6.4 The spin-density distribution of single-side hydrogenated
graphenes with top- and side-views: (a) 50% (Z), (b) 33.3%
(A), (c) 25% (Z), (d) 16.7% (A), (e) 11.1% (Z), and (f) 7.1%
(C) H-concentrations. The red isosurfaces represent the charge
density of spin-up configuration, whereas the green circles point
out the position of H atoms. . . . . . . . . . . . . . . . . . . . 72
6.5 The charge densities of (a) 50% (Z), (b) 25% (Z), (c) 33.3% (A),
(d) 7.1% (C), (e) double-side 100% (Z), and (f) double-side
6.3% (A) hydrogenated graphenes. The corresponding charge
density differences are, respectively, shown in (g–l). . . . . . . 73
6.6 The orbital-projected DOS of single-side hydrogenated graphenes
for various H-concentrations: (a) 50% (Z), (b) 33.3% (A),
(c) 25% (Z), (d) 16.7% (A), (e) 11.1% (Z), (f) 7.1% (C),
(g) 25% (Z), (h) 11.1% (Z), (i) 8.3% (A), and (j) 6.3% (Z).
The non-magnetic systems in (g)–(j) present the spin-
degenerate DOS. . . . . . . . . . . . . . . . . . . . . . . . . . 74
6.7 Geometric structures of double-side hydrogenated graphene
with top and side views for (a) 100% (Z), (b) 33.3% (A), (c)
25% (Z), (d) 14.3% (C), (e) 6.3% (Z), (f) 4% (Z), (g) 11.1%
(Z), and (h) 8.3% (A) H-concentrations. . . . . . . . . . . . . 76
6.8 Band structures of double-side hydrogenated graphenes with-
out spin polarizations: (a) 100% (Z), (b) 25% (Z), (c) 6.3% (Z),
(d) 4% (Z), (e) 2% (Z), (f) 33.3% (A), (g) 14.3% (C), and (h)
1.6% (C) H-concentrations. . . . . . . . . . . . . . . . . . . . 79
6.9 Band structures of double-side hydrogenated graphenes
with spin polarizations and their corresponding spin-density
distributions: (a) 11.1% (Z) and (b) 8.3% (A) H-
concentrations. . . . . . . . . . . . . . . . . . . . . . . . . . . 80
6.10 The orbital-projected DOS of double-side hydrogenated
graphenes: (a) 100% (Z), (b) 25% (Z), (c) 2% (Z), (d) 33.3%
(A), (e) 14.3% (C), (f) 1.6% (C), (g) 11.1% (Z), and (h) 8.3%
(A) H-concentrations. The red isosurfaces represent the charge
density of spin-up configuration, whereas the green circles point
out the position of H atoms. . . . . . . . . . . . . . . . . . . . 81

7.1 Geometric structures of halogen-doped graphene for

(a) double-side 100% (Z), (b) double-side 50% (Z), (c) 50%
(Z), (d) 25% (Z), (e) 16.7% (A), and (f) 3.1% (Z) halogen-
concentrations. . . . . . . . . . . . . . . . . . . . . . . . . . . 85
List of Figures xi

7.2 Band structures for (a) a pristine graphene, and the (b) F-, (c)
Cl-, (d) Br-, (e) I-, and (f) At-doped graphenes with concentra-
tion X:C = 1:32 = 3.1% (Z). The green circles correspond to
the contributions of adatoms, in which the dominance is pro-
portional to the radius of circle. . . . . . . . . . . . . . . . . . 87
7.3 Band structures of F-doped graphenes: (a) double-side F:C =
8:8 = 100% (Z), (b) double-side F:C = 4:8 = 50% (Z), (c) F:C
= 4:8 = 50% (Z), (d) F:C = 2:8 = 25% (Z), (e) F:C = 1:6
= 16.7% (A), and (f) F:C = 1:18 = 5.6% (Z) concentrations.
The green and red circles correspond to the contributions of
adatoms and passivated C atoms, respectively. . . . . . . . . 89
7.4 Band structures of Cl- and Br-doped graphenes: (a) double-side
Cl:C = 8:8 = 100% (Z), (b) double-side Cl:C = 4:8 = 50% (Z),
(c) Cl:C = 2:8 = 25% (Z), (d) Cl:C = 1:6 = 16.7% (A), (e)
Cl:C = 1:8 = 12.5% (Z), (f) double-side Br:C = 8:8 = 100%
(Z), (g) Br:C = 2:8 = 25% (Z), and (h) Br:C = 1:8 = 12.5%
(Z) concentrations. . . . . . . . . . . . . . . . . . . . . . . . . 90
7.5 The spin-density distributions with top and side views, for var-
ious concentrations: (a) F:C = 50% (Z), (b) F:C = 16.7% (A),
(c) Cl:C = 12.5% (Z), (d) Br:C = 12.5%, (e) Cl:C = 3.1%,
and (f) Br:C = 3.1%. The red isosurfaces represent the charge
density of spin-up configuration. . . . . . . . . . . . . . . . . 91
7.6 The charge densities of: (a) pristine graphene, (b) F:C = 8:8 =
100% (Z), (c) F:C = 2:8 = 25% (Z), and (d) F:C = 1:32 = 3.1%
(Z). The corresponding charge density differences of fluorinated
graphenes are, respectively, shown in (e–g). . . . . . . . . . . 93
7.7 The charge densities of chlorinated graphenes: (a) Cl:C = 8:8
= 100% (Z), (b) Cl:C = 2:8 = 25% (Z), and (c) Cl:C = 1:32
= 3.1% (Z). The corresponding charge density differences are,
respectively, shown in (d–f). . . . . . . . . . . . . . . . . . . . 94
7.8 Orbital-projected DOS of fluorinated graphenes for various con-
centrations: (a) double-side F:C = 100% (Z), (b) F:C = 25%
(Z), (c) F:C = 50% (Z), (d) F:C = 16.7% (A), (e) F:C = 5.6%
(Z), and (f) F:C = 3.1% (Z). . . . . . . . . . . . . . . . . . . 95
7.9 Orbital-projected DOS of Cl- and Br-doped graphenes for var-
ious concentrations: (a) double-side Cl:C = 100% (Z), (b)
double-side Cl:C = 50% (Z), (c) Cl:C = 16.7% (A), (d) Cl:C =
12.5% (Z), (e) Cl:C = 3.1% (Z), (f) double-side Br:C = 100%
(Z), (g) Br:C = 25% (Z), and (h) Br:C = 3.1% (Z). . . . . . . 96

8.1 Geometric structures of alkali-adsorbed graphene for (a) 50%

(A), (b) 16.7% (A), (c) 12.5% (Z), (d) 5.6% (Z), (e) 4.2% (A),
and (f) 3.1% (Z) alkali-concentrations. . . . . . . . . . . . . . 103
xii List of Figures

8.2 Band structures for (a) a pristine graphene, and the (b) Li-, (c)
Na-, (d) K-, (e) Rb-, and (f) Cs-adsorbed graphenes in 4 × 4
supercell. The blue circles correspond to the contributions of
adatoms, in which the dominance is proportional to the radius
of circle. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
8.3 Band structures of Li-adsorbed graphenes with various concen-
trations: (a) 50%, (b) 16.7%, (c) 12.5%, (d) 5.6%, (e) 100%, and
(f) 25%, in which the last two belong to double-side adsorption.
The blue circles correspond to the contributions of adatoms. . 107
8.4 The spatial charge distributions of Li-adsorbed graphenes with
(a) 3.1%, (b) 5.6%, (c) 50%, and (d) 100% concentrations, and
(e) K-, (f) Cs-adsorbed graphenes with 3.1% concentrations.
Those of nanoribbon systems are shown for (g) N Z = 8 and
(1)single and (h) N A = 12 and (1)single . . . . . . . . . . . . . 109
8.5 Orbital-projected DOS for (a) pristine, (b) Li-, (c) K-, and
(d) Cs-adsorbed graphenes with 3.1% concentration, and Li-
adsorbed graphene with (e) 5.6%, (f) 16.7%, (g) 50%, (h) 100%
concentrations. . . . . . . . . . . . . . . . . . . . . . . . . . . 110
8.6 Geometric structures of alkali-adsorbed graphene nanoribbons
for (a) NA = 12 armchair and (b) NZ = 8 zigzag systems.
The dashed rectangles represent unit cells used in the calcu-
lations.√The lattice constants Ix are, respectively, a = 3b and
a = 2 3b for armchair and zigzag systems. Numbers inside
hexagons denote the adatom adsorption positions. The spin
configurations of pristine, (1)single and (7)single are indicated
in (c), (d) and (e), respectively. Blue and red circles, respec-
tively, represent spin-up and spin-down arrangements. . . . . 112
8.7 Band structures of N A = 12 armchair systems for (a) a pristine,
(b) Li and (1)single , (c) K and (1)single , (d) Cs and (1)single , (e)
Li and (1,10)single , (f) Li and (3,7)single , (g) Li and (3,7)double ,
(h) Li and (1,4,7,10)double , and those of N Z = 8 zigzag systems
for (i) a pristine, (j) Li and (1)single , (k) Li and (7)single , and
(l) Li and (1,13)single . Blue circles represent the contributions
of alkali adatoms. . . . . . . . . . . . . . . . . . . . . . . . . . 113
8.8 Orbital-projected DOS in Li-adsorbed graphene nanoribbons of
N A = 12 armchair systems for (a) a pristine nanoribbon, (b)
(1)single , (c) (1,10)single , and (d) (3,7)single . Those of N Z =
8 zigzag systems are shown for (e) a pristine nanoribbon, (f)
(1)single , (g) (7)single , and (h) (1,13)single . . . . . . . . . . . . 118

9.1 Side view and top view geometric structures of aluminum-

adsorbed graphene for (a) 12.5% (A), (b) 5.6% (A), (c) 4.2%
(Z), and (d) 3.1% aluminum-concentrations. . . . . . . . . . . 121
List of Figures xiii

9.2 Band structures of (a) pristine graphene and Al-adsorbed

graphenes with various concentrations: (b) 12.5%, (c) 5.6%,
(d) 4.2%, (e) 3.1%, and (f) 25%, in which the last one belong
to double side adsorption. The blue circles correspond to the
contributions of adatoms. . . . . . . . . . . . . . . . . . . . . 123
9.3 The spatial charge distributions of Al-adsorbed graphenes with
(a) 12.5%, (b) 5.6%, and (c) 3.1% concentrations. The corre-
sponding charge density differences are, respectively, shown in
(d–f). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
9.4 Orbital-projected DOS for (a) pristine graphene and Al-
adsorbed graphenes in (b) 12.5%, (c) 5.6%, (d) 4.2%, (e) 3.1%,
and (f) 25% concentrations. . . . . . . . . . . . . . . . . . . . 125
9.5 Geometric structure of 4H-SiC (0001) substrate, buffer layer,
monolayer graphene, and bismuth adatoms. C, Si and Bi are,
respectively, indicated by the gray, yellow, and purple solid
circles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
9.6 (a) Ground-state energies of bismuth adsorption on different
sites above monolayer graphene. (b) Geometric structures of
hexagonal Bi array. . . . . . . . . . . . . . . . . . . . . . . . . 129
9.7 (a) Geometric structures of Bi nanoclusters. (b) DOS for hexag-
onal Bi array. . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
List of Tables

5.1 Optimized C–O Bond Lengths, C–C Bond Lengths, Binding

Energy (Eb ) and Energy Gap (Eg ) for Various Concentrations
of Single-Side Adsorbed GOs. . . . . . . . . . . . . . . . . . . 53
5.2 Calculated Binding Energy (Eb ) and Energy Gap (Eg ) of
Double-Side Adsorbed GOs with Various O-Concentrations. . 61

6.1 Calculated C–C and C–H Bond Lengths, H–C–C Angle, Height
(Shift on z-Axis) of Passivated C, Binding Energy, Energy Gap,
and Total Magnetic Moments per Unit Cell for Various H-
Coverages of Single-Side Adsorption. . . . . . . . . . . . . . . 68
6.2 Calculated C–C and C–H Bond Lengths, H–C–C Angles,
Heights (Shift on z-Axis) of Passivated Carbons, Bind-
ing Energy, Energy Gaps, and Total Magnetic Moments
per Unit Cell for Various H-Concentrations of Double-Side
Adsorption. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

7.1 Calculated C–C and C–X Bond Lengths, Heights (Shift on z-

Axis) of Passivated Carbons, Binding Energies, Energy Gaps,
and Total Magnetic Moments per Unit Cell of Halogen-
Absorbed Graphene Systems. . . . . . . . . . . . . . . . . . . 86

8.1 Calculated C–C and A–C Bond Lengths, Heights of Passi-

vated Carbons, Binding Energies, and Carrier Density of Li
System. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
8.2 Free Electron Densities for Various Numbers and Positions of
Adatoms In NA = 12 and Nz = 8 Alkali-Adsorbed Graphene
Nanoribbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . 115

9.1 Bond Lengths and Heights for Various Al-Adsorbed

Graphenes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
9.2 Adsorption Energies and Heights for Various Atomic
Sites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

xv
Preface

Since graphene was first synthesized in 2004, it has been extensively studied
both theoretically and experimentally. Graphene exhibits a lot of remark-
able physical, chemical, and material properties, leading to highly potential
applications in various areas. Numerous methods and techniques have been
developed to greatly diversify the essential properties, mainly based on the
changes in lattice structures, stacking configurations, doping, external elec-
tric/magnetic fields, mechanical strains, and so on.
This book aims to provide a systematic investigation on the feature-
rich essential properties in graphene-related systems, covering both up-to-
date mainstream theoretical and experimental research. It includes a wide
range of systems, namely, few-layer graphenes, sliding bilayer graphenes, rip-
pled graphenes, carbon nanotubes, graphene nanoribbons, and adatom-doped
graphenes (O-, H-, halogen-, alkali-, Al-, and Bi-doped graphenes). The sys-
tematic studies, which are focused on the structure-, stacking-, layer-, orbital-,
spin-, and adatom-created diverse properties, can greatly promote the basic
and applied sciences. Specially, the single- and multi-orbital chemical bond-
ings, being responsible for the diverse electronic properties, are explored in
detail. This point of view could be further generalized to understand the essen-
tial properties in various materials. The theoretical framework developed in
this work will be useful in the characterizations of emergent materials, because
it is thoroughly examined through detailed analyses of the rich and unique
properties. All the calculated results are mainly presented in figures, which
are obtained using the first-principles method in the accurate and delicate
form. They agree with those from other theoretical calculations (e.g., the
tight-binding model) and are validated by the experimental measurements.
In this book, we do not provide a thorough discussion of the basic under-
lying concepts that can be found in many previously published books. We try
to link and explain the various results using the basic concepts of physics and
chemistry. We have used the chemical bondings to connect all the systems;
this is understandable even at an undergraduate level if students have a back-
ground in solid-state physics and fundamental chemistry. However, this book
is primarily of interest for graduate students and researchers. Some problems
are added at the end of the book; they could be solved by the tight-binding
model in Section 3.5 and theoretical references in this work.
In summary, this book presents a systematic review on the feature-rich
essential properties of graphene-related systems using the first-principles cal-
culations. The geometric and electronic properties are greatly enriched by the

xvii
xviii Preface

different numbers of layers, the stacking configurations, the sliding-created

configuration transformations, the rippled/curved structures, and the distinct
adatom adsorptions. The top-site adsorptions can induce significantly buckled
structures, especially by hydrogen and fluorine adatoms. The electronic struc-
tures consist of the carbon-, adatom-, and (carbon, adatom)-dominated energy
bands. There exist linear, parabolic, partially flat, sombrero-shaped, and oscil-
latory bands, associated with various kinds of critical points. The semimetal-
lic or semiconducting behavior of graphene systems is dramatically changed
by the multi- or single-orbital chemical bondings between carbons/adatoms
and adatoms. Graphene oxides and hydrogenated graphenes possess tunable
energy gaps. Fluorinated graphenes might be semiconductors or hole-doped
metals, whereas other halogenated systems certainly belong to the latter.
Alkali- and Al-doped graphenes possess the high-density conduction electrons
in the preserved Dirac cones. The ferromagnetic spin configuration is revealed
in hydrogenated and halogenated graphenes under certain adatom distribu-
tions. Specifically, Bi nanostructures are formed by the significant interactions
between monolayer graphene and buffer layers. The structure- and adatom-
enriched essential properties are compared with the measured results, and
potential applications are also discussed.
We express our sincere gratitude to our colleagues who have reviewed
and/or made comments to this book. This work was supported by the National
Center for Theoretical Sciences (South) and the Nation Science Council of
Taiwan, under the grant No. NSC 102-2112-M-006-007-MY3. We also thank
the National Center for High-performance Computing Taiwan for computer
time and facilities. Last but not least, we express our thanks to Florence
Kizza, Allison Shatkin, Teresita Munoz, Suchita Chadha, and other staff of
CRC Press for the pleasant collaboration and guidance.
Authors

Ngoc Thanh Thuy Tran obtained her

PhD in physics in January 2017 from the
National Cheng Kung University (NCKU),
Tainan, Taiwan. Immediately after finishing
her PhD, she began to work as a postdoctoral
researcher at NCKU. Her scientific interest is
focused on the functionalization of graphene
and its derivatives using first-principle calcu-
lations.

Shih-Yang Lin received his PhD in physics

in 2015 from the National Cheng Kung Uni-
versity (NCKU), Taiwan. Since 2015, he has
been a postdoctoral researcher at NCKU. His
research interests include low-dimensional
group IV materials and first-principle calcu-
lations.

Chiun-Yan Lin obtained his PhD in 2014 in

physics from the National Cheng Kung Uni-
versity (NCKU), Tainan, Taiwan. Since 2014,
he has been a postdoctoral researcher at
NCKU. His main scientific interests are in the
field of condensed matter physics, and model-
ing and simulation of nanomaterials. Most of
his research is focused on the electronic and
optical properties of two-dimensional nano-
materials.

xix
xx Authors

Ming-Fa Lin is a distinguished profes-

sor in the department of physics, National
Cheng Kung University, Tainan, Taiwan. He
received his PhD in physics in 1993 from
the National Tsing-Hua University, Hsinchu
City, Taiwan. His main scientific interests
focus on the essential properties of carbon-
related materials and low-dimensional sys-
tems. He is a member of the American Phys-
ical Society, the American Chemical Society,
and the Physical Society of Republic of China
(Taiwan).
1
Introduction

There are condensed-matter systems purely constructed from carbon atoms,

including diamond [1], graphites [2,3], graphenes [4,5], graphene nanoribbons
[6–8], carbon nanotubes [9–11], carbon toroids [12,13], C60 -related fullerenes
[14,15], and carbon onions [16,17]. Such systems are formed in various dimen-
sions by the very active bondings related to the four atomic orbitals; further-
more, the versatile morphologies suggest the existence of peculiar phenomena.
All of the carbon-related systems possess sp2 -bonding surfaces except for the
sp3 bonding in diamond. Specifically, the few- and multilayer graphenes have
been manufactured using various methods since the first discovery in 2004 by
the mechanical exfoliation [4]. Graphene exhibits a lot of remarkable essential
properties arising from the hexagonal symmetry and the nanoscale size, such
as an anomalous quantum Hall effect [18,19], an exceedingly high mobility of
charge carriers [20,21], a high transparency [22,23], the largest Young’s modu-
lus of materials ever tested [24,25], diverse optical selection rules [26,27], rich
magnetic quantization [28,29], unusual plasmon modes [30,31], and semicon-
ducting and semimetallic behavior [32–34]. To create novel phenomena and
extend the potential applications, the electronic properties can be easily mod-
ulated by the layer number [35,36], stacking configuration [33,36], mechanical
strain [37,38], sliding [39,40], doping [41,42], electric field [32,43–45], magnetic
field [46,47], and temperature [48,49]. This book focuses on the layer number-,
stacking-, shift-, ripple- and doping-dependent geometric structures and elec-
tronic properties by using first-principles calculations. The structure-enriched
graphenes, graphene oxides (GOs), hydrogenated graphenes, and halogen-,
alkali-, Al- and Bi-doped graphenes are taken into consideration. The physi-
cal and chemical pictures, especially with regard to the multi-orbital chemical
bondings, are provided to better comprehend the newly created phenomena.
The orbital hybridizations among the same/distinct atoms, which account for
the main features of the electronic structures, are explored in detail; e.g., the
effects of chemical bondings on the Dirac-cone structures, energy gaps, semi-
conducting, semimetallic and metallic behavior, adatom-dependent energy
bands, free electrons and holes, spatial charge distributions, specific adatom
nanosclusters, and special structures in the density of states (DOS). Spin con-
figurations are another focus on hydrogenated and halogenated graphenes.
A detailed comparison with other theoretical studies and experimental mea-
surements is made. The high potential of the various materials for applications
are also discussed.

1
2 1 Introduction

The stacking symmetry plays a critical role in the essential properties of

layered graphenes. The pristine graphenes, with the stacking order [50–58] or
the turbostratic structure [59–61], have been observed by the various exper-
imental methods. In general, the stacking configurations are presented in
the forms of AAA, ABA, ABC and AAB (Figure 3.1). These typical sys-
tems exhibit different characteristics in electronic properties [62–67], magnetic
quantization [29,67–69], optical excitations [43,70–72], transport properties
[73–76], and phonon spectra [77–80]. The electronic structures are extensively
investigated by the first-principles calculations [81–84] and the tight-binding
model [29,67,68,85]. These studies show that the interlayer atomic interactions
of carbon 2pz orbitals dominate the low- and middle-energy electronic struc-
ture. The main energy bands—the linear, parabolic, partially flat, sombrero-
shaped and oscillatory ones—depend on the stacking configurations. The
important stacking-induced differences in energy dispersions can diversify the
quantization phenomena, selection rules, Hall conductances and Raman spec-
tra. For example, the magnetoelectronic properties of the higher-symmetry
AAA stacking have the monolayer-like quantized Landau levels (LLs) with
the well-behaved modes [29], while those of the lower-symmetry AAB stack-
ing present the splitting LLs and the frequently anti-crossing behavior [67]. On
the experimental side, scanning tunneling microscopy (STM) [50,55], angle-
resolved photoemission spectroscopy (ARPES) [52,53,86–88], and scanning
tunneling spectroscopy (STS) are [89–95], respectively utilized to verify geo-
metric structures, band structures, and DOS. Up to now, the experimen-
tal measurements have identified the interlayer distance of 3.55 Å (3.35 Å)
in AA (AB) stacking [50,55], the Dirac-cone structure in monolayer system
[53,86,87], the parabolic dispersions in bilayer AB stacking [53,88], the linear
and parabolic bands in tri-layer ABA stacking [52,53], the weakly dispersive,
sombrero-shaped and linear bands in tri-layer ABC stacking [52], and a lot of
stacking- and layer-enriched van Hove singularities in DOS [89–95].
One of the mainstream topics in pristine graphenes is how to create the
dramatic transitions of essential properties. The critical factors are the obvi-
ous changes in geometric structures, such as the electrostatic manipulation
of scanning tunneling microscopy (STM) on stacking symmetry [56,96–98]
and the successful synthesis of graphene ripple using chemical vapor depo-
sition (CVD) [99–101]. The sliding bilayer graphene and monolayer rippled
graphene are suitable for a model study. The former has been studied in the
electronic [39,40], magnetic [102], optical [72,103], transport [104] and phonon
[105] properties. The transformation between two specific stacking configura-
tions will induce the continuous variation in the interlayer atomic interactions
of 2pz orbitals and thus lead to the diverse/unique physical phenomena. For
example, two isotropic Dirac-cone structures are transformed into two pairs
of parabolic bands during AA→AB [39,40]. Furthermore, the sliding bilayer
graphene exhibits three kinds of LLs (the well-behaved, peturbed and unde-
fined LLs) and three magneto-optical selection rules of ∆ n = 0, ± 1 and ± 2
(n: the quantum number for each LL) [102,106]. As for rippled graphenes,
1 Introduction 3

the charge distribution of carbon four orbitals becomes highly non-uniform

on a curved surface. The sp2 bonding is dramatically changed into the sp3
bondings in the increase of curvature. The theoretical calculations show that
the curvature effects, the misorientation of 2pz orbitals and hybridization of
(2s, 2px , 2py , 2pz ) orbitals dominate the essential properties, e.g., the seriously
distorted Dirac cone and the semiconductor-semimetal transition [107,108].
The similar effects are clearly revealed for 1D carbon nanotubes, e.g., the
largely reduced energy gaps in zigzag nanotubes [109–111] and the metallic
ones with very small radii [112,113]. However, the distinct dimensions and
boundary conditions will account for the main differences between rippled
graphenes and carbon nanotubes. The position-dependent STS measurements
on graphene ripple are made to explore the relation between curvatures and
electronic structures [99–101], e.g., the V-shaped spectrum and many special
structures in the differential conductance. The curvature-induced charge dis-
tribution provides an available chemical environment for potential materials
applications.
The chemical modification on graphene surface is emerging as a useful
tool to engineer new electronic properties. The adatom adsorption is a very
efficient method in generating the gap-tunable semiconductors and the 2D
metals with high free carrier density. All the pristine graphenes exhibit the
gapless or narrow-gap behaviors in the absence and presence of external fields
[32,43–47], which clearly illustrates the high barriers in gap engineering. The
significant gap opening in the electronic properties is an important issue for
the future nanoelectronic and optical devices. GOs are qualified as a poten-
tial candidate, since their energy gaps can be straightforwardly modulated
by different distributions and concentrations of oxygen adatoms. GOs have
been successfully synthesized by the distinct chemical processes, especially for
the four methods developed by Brodie [114], Staudenmaier [115], Hummers
[116], and Tang [117]. Three kinds of chemical bonds, C–O, O–O and C–C
bonds, are formed in GOs, as indicated by several theoretical studies [118–122].
Apparently, the atomic interactions of carbon 2pz orbitals are not the criti-
cal factors in determining the essential properties. The comprehensive orbital
hybridizations, which are responsible for the gap opening and the rich elec-
tronic properties, are worthy of a systematic investigation. The first-principles
calculations show that the atom- and orbital-related hybridizations could be
analyzed by means of the atom-dominated energy bands, the spatial charge
distributions, and the orbital-projected DOS [118,119]. Such hybridizations
are very useful in understanding the relation between the forms of chemi-
cal bondings and the concentration-dependent energy gaps, and the drastic
oxidization-induced changes of band structures. For example, various chemi-
cal bondings can destroy the Dirac cone and generate the O-, C- and (C,O)-
dominated energy bands with many van Hove singularities. Energy gaps in
the absence of Dirac cone are confirmed by the ARPES [123] and STS [124]
measurements. GOs present the diverse chemical environments suitable for
materials engineering.
4 1 Introduction

Graphane, a 2D hydrocarbon compound with the extended covalent C–H

bonds, is first proposed by Sofo et al. [125]. In general, hydrocarbon sys-
tems are good fuel materials because they can be readily oxidized to generate
carbon dioxides and water with considerable energy release. Graphane is pre-
dicted to be a wide-gap semiconductor of Eg ∼ 3.5 eV. Energy gaps are easily
modulated by the changes of the concentration and distribution of H adatoms
[126–129]; therefore, hydrogenated graphenes are very suitable for essential
science and technical applications. The chemical adsorption of H adatoms on
graphene surface is successfully produced by hydrogen plasma under electrical
discharge [130,131], electron irradiation of adsorbates (H2 O and NH3 ) [132],
plasma-enhanced CVD [133], and photohydrosilylation reactions [134]. The
hydrogen concentration can be estimated from the intensity ratio of D and
G bands in Raman spectroscopy [130,131]. Moreover, the hydrogen adatom-
induced energy gap is verified from the ARPES [135,136] and STS measure-
ments [137,138]. This clearly illustrates that hydrogen adatoms have strong
chemical bondings with carbon atoms, even if the former possess only one
1s orbital. Their locations are revealed to be at the top sites as predicted
by simulations [125–129] and identified by experiments [139]. These optimal
adsorption positions can create an obvious buckling of a hexagonal struc-
ture corresponding to the various bond lengths and angles. The curvature
effects will lead to the drastic changes of carbon sp2 bondings and thus the
extra orbital hybridizations. In addition to the rich geometric and electronic
properties, the theoretical calculations present the non-magnetic and mag-
netic properties, which strongly depend on the hydrogen distribution [140].
Hydrogenated graphenes might exhibit the splitting of spin-up and spin-down
energy bands. Such electronic states in transport measurements are expected
to produce the spin-polarized currents, indicating potential applications in
spintronic devices [128,141–144].
Halogen atoms have very strong electron affinities, meaning that significant
chemical bondings with carbon atoms can create dramatic changes of essen-
tial properties. They are ideal adsorbates on graphene surface for the study
on intricate and versatile phenomena. It is very desirable to systematically
investigate whether five kinds of halogen adatoms will possess similar features
or present important differences. Fluorinated graphenes have been success-
fully synthesized by the fluorination methods of direct gas [145,146], plasma
[147,148], photochemistry [149,150] and hydrothermal reaction [151,152]. A lot
of experimental [153,154] and theoretical [155,156] studies show that such sys-
tems belong to the unusual semiconductors or the p-type metals, depending on
the fluorination conditions. Large energy gaps due to the high fluorination are
clearly evidenced in the experimental measurements of electrical resistances
[145,153], optical transmissions [153,154], and photoluminscence spectra [154].
Furthermore, the p-type doping is identified by the redshift of the Fermi
level from ARPES measurements [157]. The tunable electronic properties
clearly indicate the potential applications in various areas, e.g., lithium bat-
teries [158], supercapacitors [159], biological scaffold materials [160], printing
1 Introduction 5

technologies [161], molecule detectors [162], and biosensors [163]. Specifically,

the theoretical calculations predict the ferromagnetic behavior [164], while
the measured magnetic moment presents the temperature-dependent para-
magnetism [165]. This difference might be due to the non-uniform adatom
clusters formed in rippled graphene. Experimental synthesis also exists on the
chlorinated [166,167], brominated [168], and iodinated [169] graphenes. From
less than a few theoretical calculations [155,156], the geometric, electronic and
magnetic properties of the (Cl, Br, I, At) absored graphenes are predicted to
be in sharp contrast with the fluorinated systems. The main differences might
lie in the critical orbital hybridizations of the halogen–C bonds. Except for
the fluorinated graphene, the rest of the halogen-absorbed systems have many
free holes for arbitrary adatom distribution and concentration as confirmed
by the upshift of the graphitic G-band phonon [167].
Because each of them possesses an s-state electron in the outmost orbital,
alkali atoms can create active chemical environments to form critical inter-
actions with other atoms or molecules. The significant interactions between
graphene-related systems and alkali-metal atoms have long been intensively
investigated, such as graphite intercalation compounds [170], and alkali-doped
carbon nanotubes [171,172], graphenes [88,173], and fullerenes [174,175].
Alkali atoms are very efficient n-type chemical dopings, as they are inter-
calated within graphitic layers and adsorbed on hexagonal surfaces. The
alkali-induced free electrons are rather suitable for studying the diverse
quasiparticle phenomena in the different dimensional systems [87]. Potas-
sium [87,88,173,176], lithium [177], sodium [178], rubidium [179], and cae-
sium [179] adatoms have been successfully utilized to chemically dope pristine
graphene systems. The tunable conduction electron density is directly con-
firmed by ARPES [87,88,178,180,181]. The alkali-adsorbed graphenes present
an obvious red shift in the Dirac-cone structure, as revealed by experimental
and theoretical investigations [182–185]. The critical orbital hybridizations in
alkali-carbon interactions could be understood from the detailed analyses of
the first-principles calculations. They determine where the carbon- and alkali-
dominated energy bands come to exist [185]. For example, depending on the
free carrier density the occupied conduction electrons can be related to both
energy bands or just the carbon-dominated one. Although the evaluation of 2D
free carrier density is an important topic, an accurate assessment is difficult to
obtain from energy bands within the first Brillouin zone. The alkali-adsorbed
graphene nanoribbons are introduced to see how many electrons contributed
by alkali adatoms become free conduction carriers, mainly due to a linear rela-
tionship between the Fermi momentum and the 1D carrier density. A system-
atic study predicts that each alkali adatom contributes the outermost s-state
orbital to build the Fermi sea through the critical interactions. Specifically, the
free-carrier density is linearly proportional to the adatom concentration, but
independent of the edge structure, the ribbon width and the kind and distri-
bution of alkali atoms. In the first-principles calculations, the Bader analysis
is frequently used to judge the charge transfer between two different atoms.
6 1 Introduction

Whether this method is suitable in calculating the free-carrier density will

be discussed in Chapter 8. The very high free-carrier density generated by
alkali adatoms in graphene-related systems is very useful in developing next-
generation nanoelectronic devices [186,187].
Al atoms possess three valence electrons in their outer shells, creating
the active chemical environments where strong interactions with elements
such as carbon, hydrogen, silicon and some heavy metals take place. The-
oretical studies show that the most stable adsorption of Al adatoms on a
graphene surface is located at the hollow site [182,188]. As the alkali-doped
systems, the Al-doped graphenes are predicted to present n-type doping char-
acteristics [182,185]. Their similarities also extend to comparable DOS at the
Fermi level and their free electron density [185]. At room temperature the
Al-subsituted systems might serve as potential hydrogen storage materials,
where the functional capacity is largely enhanced by the Al atoms due to the
strong Al–C bonds [189]. Carbon monoxide could be detected by the drastic
changes in electrical conductivity during the process of molecule adsorption
[190], because of more valence electrons from Al atoms. On the experimental
side, Al-related molecules exhibit significant chemical reactions. A practical
example is the high-performance rechargeable aluminium-ion battery [191].
Specifically, layered graphene systems are frequently grown on various sub-
strates, such as the widely used silicon carbide, Au and Ag metals. Controlling
the adatom nano-structures by the critical interactions between adsorbates
and substrates is very important in the fabrication of low-dimensional materi-
als with unique electronic properties. Recently, the corrugated substrate and
the buffer graphene layer have been observed by STM [192,193]. A large-scale
hexagonal array of Bi atoms is clearly revealed at room temperature, while
such adatoms are aggregated in triangular and rectangular nanoclusters as
a meta-stable structure during the annealing process. The characteristics of
high structural stability and tunable adatom distributions are very useful in
developing next-generation nanoelectronic devices.
This book broadly covers the fields related to graphene systems in the
forms of few-layer AAA, ABA, ABC, AAB stackings, sliding and rippling
configurations, and dopings with various adatoms. Furthermore, it investi-
gates many of the factors affecting the geometric and electronic properties,
e.g., the hexagonal symmetry, mirror/inversion symmetry, rotational symme-
try, stacking configuration, curvature, boundary condition, adatom distribu-
tion and concentration, charge transfer, orbital hybridization, spin arrange-
ment and buffer layer/substrate. The optimal geometric structures focus on
the interlayer distance, bond length, bond angle, critical curvature, position
and height of adatom and nanostructure of adatom. The main features of
energy bands are revealed in the contribution of atom, energy dispersion,
existence of Dirac cone, isotropy or anisotropy, symmetry or asymmetry
about EF , energy gap, critical point, constant-energy surface, state degen-
eracy, and spin-induced splitting. The aforementioned 2D critical points can
exhibit the special structures in DOS, including the V-shaped form, shoulders,
1 Introduction 7

asymmetric peaks, and symmetric peaks. In addition to the essential proper-

ties, materials functionalities and potential applications are also discussed.
The details of computational methods are provided in Chapter 2. In Chap-
ter 3, the stacking-enriched electronic properties are studied for four kinds of
tri-layer graphenes, in which the similarities and differences are explored in
detail. Discussions on the consistence with the ARPES, STM, and STS mea-
surements and the further examinations are made. Chapter 4 discusses the
dramatic transformations of electronic structures which could be observed by
sliding in bilayer graphene and rippling in monolayer graphene. The effects
arising from the interlayer atomic interactions and the non-uniform charge
distribution on a curved surface deserve a systematic investigation, especially
for the semiconductor-semimetal transition in rippled graphenes. A discus-
sion of strong sp3 hybridizations and boundary conditions, carbon nanotubes
is found in Section 4.2. Chapters 5 through 9, respectively, describe O-,
H-, halogen-, alkali-, and Al- and Bi-doped graphenes. Detailed reports are
made to analyze the atom-dominated energy bands, spatial distributions for
total charges and charge differences, magnetic configurations, and total and
orbital-projected DOS. The complex orbital hybridizations are obtained for
various adatoms. Five types of π bondings are proposed to account for the
concentration-dependent energy gaps in semiconducting GOs. Being sensi-
tive to the changes of distribution and concentration, the significant orbital
hybridizations in C–H and C–C bonds induce the middle, narrow and zero
gaps. The spin-split energy bands are examined for the H-, Cl- and Br-doped
graphenes. The strong affinity of halogen adatoms can create free holes, while
the F-doped systems might become semiconductors at sufficiently high con-
centration. The metal-semiconductor transition is associated with the com-
plex multi-orbital hybridizations. On the other hand, because the alkali-doped
graphenes are insensitive to the distinct adatoms, they have high free electron
densities. The explored relationship between the π bonding and the adatom-
carbon hybridization is explored to comprehend why the red-shift Dirac-cone
structures are observed in alkali- and Al-doped graphenes. The alkali-doped
graphene nanoribbons are introduced to accurately evaluate the free carrier
densities. Specifically, for Bi-doped graphene, the six-layered substrate, corru-
gated buffer layer, and slightly deformed monolayer graphene are all simulated.
The transformation from the most stable hexagonal array to the meta-stable
nanocluster is determined by the interactions between buffer layer and mono-
layer graphene. Finally, Chapter 10 contains concluding remarks and future
outlook.
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death from which she wished to save that father’s brother. The duke
was civil and compassionate, but would make no promise. In fact, it
was resolved that the younger brother of the Earl of Derwentwater
should die, lying as he did under the guilt of double rebellion. ‘If I am
to die,’ said Radcliffe, splenetically, ‘Lord Morton ought to be
executed at Paris, on the same day.’ Morton was a gossiping tourist,
who, being in Brittany, made some idle reflections on the defences of
Port L’Orient in a private letter, which the French postal authorities
took the liberty to open. This brought the writer into some difficulty in
France, but as no harm was meant, Lord Morton suffered none.
The ever-to-be-amused public were not left without TO
diversity of grim entertainment between the KENNINGTON
condemnation of Radcliffe and the execution of his COMMON.
sentence. On Friday, November 28th, there was the
strangling (with the other repulsive atrocities), of five political
prisoners, on Kennington Common, in the morning, and the revival of
a play (which had years before been condemned because of the
political opinions of the author), in the evening. In the morning, two
sledges stood ready for the dragging of eight prisoners from the New
Prison, Southwark, to the gallows, disembowelling block, and fire, on
the Common. This was not an unfrequent spectacle; and on this
occasion, as on others, there was, without cowardly feeling, a certain
dilatoriness on the part of the patients, who never knew what five
minutes might not bring forth. Sir John Wedderburn, indeed, went
into the foremost sledge, with calm readiness, and Governor (of
Carlisle) Hamilton stept in beside him. Captain Bradshaw stood
apart, hoping not to be called upon. There was a little stir at the gate
which attracted feverish attention on the part of the patients.—‘Is
there any news for me?’ asked Bradshaw, nervously. ‘Yes,’ replied a
frank official, ‘the Sheriff is come and waits for you!’ Bradshaw had
hoped for a reprieve; but hope quenched, the poor fellow said he
was ready. Another Manchester Captain, Leath, was equally ready
but was not inclined to put himself forward. Captain Wood, after the
halter was loosely hung for him around his neck, called for wine,
which was supplied with alacrity by the prison drawers. When it was
served round, the captain drank to the health of the rightful king,
James III. Most lucky audacity was this for Lindsay, a fellow officer
from Manchester, bound for Kennington. While the wine was being
drunk, Lindsay was ‘haltering,’ as the reporters called it. He was nice
about the look of the rope, but just as he was being courteously
invited to get in and be hanged, a reprieve came for him, which
saved his life. Two other doomed rebels, for whom that day was to
be their last, had been reprieved earlier in the morning, and that was
why the puzzled spectators, on the way or at the place of sacrifice,
were put off with five judicial murders when they had promised
themselves eight.
In the evening, the play which was to tempt the CIBBER’S
town was a revival of Cibber’s ‘Refusal, or the Ladies’ ‘REFUSAL.’
Philosophy.’ It had not been acted for a quarter of a
century (1721), when it had failed through the opposition of the
Jacobites, who damned the comedy, by way of revenge for the satire
which Cibber had heaped on the Nonjurors. Now, the play went
triumphantly. No one dared,—when the hangman was breathless
with over-work, and the headsman was looking to the edge of his
axe, for the ultimate disposal of Jacobites,—to openly avow himself
of a way of thinking which, put into action, sent men to the block or
the gallows. All that could be done in a hostile spirit was done,
nevertheless. The Jacks accused Cibber of having stolen his plot
from predecessors equally felonious; but they could not deny that the
play was a good play; and they asserted, in order to annoy the Whig
adaptor, that the Witling of Theophilus Cibber was a finer touch of art
than that of his father in the same part.
On the 8th of December, Charles Radcliffe closed EXECUTION
the bloody tragedies of the year, with his own. He OF
came from the Tower like a man purified in spirit, RADCLIFFE.
prepared to meet the inevitable with dignity. They who
had denied his right to call himself a peer, allowed him to die by the
method practised with offenders of such high quality. The only bit of
bathos in the scene on the scaffold was when the poor gentleman
knelt by the side of the block, to pray. Two warders approached him,
who took off his wig, and then covered his head with a white skull
cap. His head was struck off at a blow, except, say the detail-loving
newspapers, ‘a bit of skin which was cut through in two chops.’ The
individual most to be pitied on that December morning was
Radcliffe’s young son, prisoner in the Tower, who was still believed
by many to be the brother of the young Chevalier.
There was another prisoner there whose life was in peril; namely
Simon, Lord Lovat. The progress up to London of Lovat and of the
witnesses to be produced against him was regularly reported. There
was one of the latter who hardly knew whether he was to be traitor or
witness, Mr. Murray of Boughton. The following describes how he
appeared on his arrival at Newcastle, and is a sample of similar
bulletins. ‘July 17th. On Thursday Afternoon, arrived here in a Coach
under the Care of Lieutenant Colonel Cockayne, escorted by a Party
of Dragoons, John Murray, Esq., of Boughton, the Pretenders
Secretary, and yesterday Morning he proceeded to London. He
seem’d exceedingly dejected and looked very pale.’
The London papers sketched in similar light LOVAT’S
touches the progress of Lovat. In or on the same PROGRESS.
carriage in which he sat were other Frasers, his
servants or retainers who, as he knew, were about to testify against
him, and whose company rendered him extremely irritable. The
whole were under cavalry escort, travelling to London, only by day.
On the morning Lovat left his inn at Northampton, the landlady was
not there to bid him farewell. The old gallant enquired for her. He
was told that she was unavoidably absent. ‘I have kissed,’ said he,
‘every one of my hostesses throughout the journey; and am sorry to
miss my Northampton landlady. No matter! I will salute her on my
way back!’ On Lovat’s arrival at St. Albans, Hogarth left London, for
what purpose is explained in part of the following advertisement,
which appears in the papers under the date of Thursday, August
28th. ‘This day is published, price one shilling, a whole length print of
Simon Lord Lovat, drawn from the life and etch’d in Aqua fortis, by
Mr. Hogarth. To be had at the Golden Head, in Leicester Fields, and
at the Print shops. Where also may be had a Print of Mr. Garrick in
the character of Richard III., in the first scene, price 7s. 6d.’
On the day on which the above advertisement HOGARTH’S
appeared, the Rev. Mr. Harris enclosed one of the PORTRAIT OF
sketches of Lovat in a letter to Mrs. Harris, written in LOVAT.
Grosvenor Square, in which he says:—‘Pray excuse my sending you
such a very grotesque figure as the enclosed. It is really an exact
resemblance of the person it was done for—Lord Lovat—as those
who are well acquainted with him assure me; and, as you see, it is
neatly enough etched. Hogarth took the pains to go to St. Albans,
the evening that Lord Lovat came thither in his way from Scotland to
the Tower, on purpose to get a fair view of his Lordship before he
was locked up; and this he obtained with a greater ease than could
well be expected; for, in sending in his name and the errand he came
about, the old lord, far from displeased, immediately had him in,
gave him a salute and made him sit down and sup with him, and
talked a good deal very facetiously, so that Hogarth had all the
leisure and opportunity he could possibly wish to have, to take off his
features and countenance. The portrait you have may be considered
as an original. The old lord is represented in the very attitude he was
in while telling Hogarth and the company some of his adventures.’
The old roystering Lovelace who kissed his ARRIVAL AT
hostesses on his way up, and talked of saluting them THE TOWER.
on his way back, was so infirm that to descend from
his carriage he leaned heavily on the shoulders of two stout men,
who put their arms round his back to keep him from falling. As he
crossed Tower Hill he came suddenly on the partly dismantled
scaffold on which the two lords had recently suffered; and he was
heard to mutter something as to his perception of the way it was
intended he should go. But, on being lifted from the carriage, he said
to the lieutenant, ‘If I were younger and stronger, you would find it
difficult to keep me here.’—‘We have kept much younger men here,’
was the reply. ‘Yes,’ rejoined Lovat, ‘but they were inexperienced;
they had not broke so many gaols as I have.’ The first news
circulated in London after Murray, the Chevalier’s ex-secretary, had
passed into the same prison, was that he had given information
where a box of papers, belonging to the Pretender, was buried, near
Inverness. A couple of king’s messengers riding briskly towards the
great North Road were taken to be those charged with unearthing
the important deposit.
 Of the two prisoners,—one was eager to save his life by giving all
the information required of him. The other, equally eager, pleaded his
innocence, his age, and his debility; but apart from declaring that he
was a loyal subject, and that he willingly had no share in the
rebellion, although his son had, he remained obstinately mute to all
questioning, or he answered the grave queries with senile banter.
Murray yielded at the first pressure. As early as REBELS AND
July, Walpole speaks of him as having made ‘ample WITNESSES.
confessions, which led to the arrest of the Earl of
Traquair and Dr. Barry; and to the issuing of warrants for the
apprehension of other persons whom Murray’s information had put in
peril. Walpole believed that the Ministry had little trustworthy
knowledge of the springs and conduct of the rebellion, till Murray sat
down in the Tower and furnished them with genuine intelligence.
While he and Lord Lovat were travelling slowly by land to the
Tower, traitors were coming up, by sea, to depose against him, or
any other, by whose conviction they might purchase safety. The
‘General Advertiser’ announced the arrival in London (from a ship in
the river) of six and twenty ‘Scotch rebels,’ who were conducted to
the Plaisterer’s Corner, St. Margaret’s Lane, Westminster, where
they were kept under a strong military guard. ‘They are brought up,’
says the above paper, ‘as evidences for the king. Several of them
are young. Some have plaids on; others in waistcoats and bonnets,
and upon the whole make a most despicable and wretched figure.’
Meanwhile Lovat struggled hard for the life he affected to despise,
and which he tried to persuade his accusers was not worth the
taking. He kept them at bay, for months, by his pleas; and he
vehemently declared his innocence of every one of the seven heads
of accusation brought against him,—of every one of which he was
certainly guilty. Towards the close of December, he was arraigned at
the bar of the House of Lords. There is no better condensation of
what took place than that furnished by Walpole, on Christmas Day,
1746:—‘Old Lovat has been brought to the bar of the House of
Lords. He is far from having those abilities for which he has been so
cried up. He saw Mr. Pelham at a distance, and called to him, and
asked him, if it were worth while to make all this fuss to take off a
grey head fourscore years old. He complained of his estate being
seized and kept from him. Lord Granville took up this complaint very
strongly, and insisted on having it enquired into. Lord Bath went
farther and, as some people think, intended the duke; but I believe
he only aimed at the Duke of Newcastle.... They made a rule to order
the old creature the profits of his estate till his conviction. He is to put
in his answer on the 13th of January.’
In the meantime, the papers reported that there TILBURY
were nearly four hundred Scottish rebels cooped up FORT.
in Tilbury Fort. Watermen’s arms were weary with
rowing boats full of Londoners down to the fort, to visit the wretched
captives, or to stare at the fort which held them in. Most of them
were transported to the Plantations. There was a sanguinary feeling
against all such offenders. The last words in the ‘General Advertiser’
for December 31st, 1746, are contained in the two concluding lines
of a poem, signed ‘Williamite,’ and which are to the following
charitable effect:—
A righteous God, with awful hands,
In justice, Blood for Blood demands.
At the same time a print was selling which represented ‘Temple
Bar, the City Golgotha,’ with three heads on the spikes,—allegorical
devils, rebel flags, &c.,—and more ‘blood for blood’ doggrel
intimating that the naughty sons of Britain might there see ‘what is
rebellion’s due.’
The idea of altogether sacrificing Charles Edward FRENCH IDEA.
was as distasteful to his numberless friends in
France, as it was to the English Jacobites. One of the most singular
of the French suggestions for a definite arrangement was made to
this effect, in some of the French papers, namely:—that George II.
should withdraw to his electorate of Hanover, taking his eldest son
and heir with him; renouncing the English crown for himself and
successors, of the elder line, for ever;—that the Chevalier de St.
George should remain as he was;—that the Prince Charles Edward
should be made King of Scotland and Ireland;—and that the Duke of
Cumberland should, as King of England, reign in London. It was a
thoroughly French idea,—making a partition of the United Kingdom,
and establishing the duke in the metropolis to reign over a powerless
fragment of it,—a Roi de Cocagne! Both political parties laughed at it
in their several houses of entertainment.
The Prince of Wales, himself, was something of a Jacobite; but he
was a Jacobite for no other reason, probably, than because his
brother, the Duke of Cumberland, had crushed the Jacobite cause. It
is due to the Prince, however, to notice that he once solemnly
expressed his sympathy when the Princess, his wife, had just
mentioned, ‘with some appearance of censure,’ the conduct of Lady
Margaret Macdonald, who harboured and concealed Prince Charles
when, in the extremity of peril, he threw himself on her protection.
‘And would not you, Madam,’ enquired Prince Frederick, ‘have done
the same, in the same circumstances? I am sure,—I hope in God,—
you would.’ Hogg relates this incident in the introduction to his
‘Jacobite Relics,’ and it does honour to the prince, himself,—who
used at least to profess fraternal affection, if not political sympathy,
by standing at an open window at St. James’s overlooking the Park,
with his arm round the Duke of Cumberland’s neck.
Frederick, however, was not a jot more acceptable A LONDON
to the Jacobites, because he was on bad terms with ELECTOR’S
the king, and that he refrained from paying any other WIT.
compliment than the above-named one to the Duke of
Cumberland, on his victory at Culloden. The prince invariably came
off, more or less hurt, whenever he engaged personally in politics.
When his sedan-chair maker refused to vote for the prince’s friend,
Lord Trentham, a messenger from his royal highness’s household
looked in upon the elector, and bluntly said, ‘I am going to bid
another person make his royal highness a chair!’ ‘With all my heart!’
replied the chair maker, ‘I don’t care what they make him, so they
don’t make him a throne!’ Again, on that day which all Tories kept as
an anniversary of crime and sorrow, the 30th of January,—‘the
martyrdom of King Charles,’ the prince entered a room where his
sister Amelia was being tended by her waiting woman, Miss Russell,
who was a great grand-daughter of Oliver Cromwell. Frederick said
to this lady, sportively, ‘Shame, Miss Russell, why have you not been
to Church, humbling yourself, for the sins on this day committed by
your ancestors?’ To which she replied, ‘Sir: I am a descendant of the
great Oliver Cromwell. It is humiliation sufficient to be employed, as I
am, in pinning up your sister’s tail!’
During the early months of 1747, the Londoners TRIAL OF
waited with impatience for the trial of Lord Lovat. The LOVAT.
old rebel had exhausted every means of delay. The
time of trial came at last. On the 9th of March, Lovat was taken from
the Tower to Westminster Hall. An immense crowd lined the whole
way, and the people were the reverse of sympathetic. One woman
looked into his coach, and said: ‘You ugly old dog, don’t you think
you will have that frightful head cut off?’ He replied, ‘You ugly old
——, I believe I shall!’ Lovat was carried through the hall in a sedan-
chair, and to a private room, in men’s arms. Mr. Thomas Harris,
writing of the trial next day, from Lincoln’s Inn, says:—‘It was the
largest and finest assembly I ever saw: the House of Commons on
one side; ladies of quality on the other, and inferior spectators
without number, at both ends.’—After much pantomimic ceremony
on the part of officials, Lovat, having been brought in, knelt (as he is
described to have done on each of the nine days of the trial). On
each occasion Lord Hardwicke solemnly said to him, ‘My Lord Lovat,
your Lordship may rise.’ On the opening day, the prosecuting
managers of the impeachment sent up by the Commons, ‘went at
him,’ at dreary, merciless, length. After them, the prosecuting
counsel opened savagely upon him, especially Murray, the Solicitor-
General, whose chief witness was his own Jacobite brother, and who
was himself suspected of having drunk the Pretender’s health on his
knees. Lovat lost no opportunity of saving his life. He
SCENE IN
pitifully alluded to his having to rise by 4 o’clock, in WESTMINSTE
order to be at Westminster by 9. He spoke of his R HALL.
frequent fainting fits; he often asked leave to retire,
and, in short, he so exasperated the Lord High Steward as to make
that official grow peevish, and to wrathfully advise Lord Lovat to keep
his temper. When the Attorney-General called his first witness,
Chevis of Murtoun, the lawyer described him, with solemn
facetiousness, as being as near a neighbour as man could be to
Lovat, but as far apart from him as was possible in thought and
action. Lovat protested against the legal competency of the witness,
he being Lovat’s tenant and vassal. Hours were spent over this
objection, and the old lord wearied the clerk, whom he called upon to
read ancient Acts of Parliament, from beginning to end. The protest
was disallowed; and the witness having been asked if he owed Lovat
money, and if a verdict of guilty might help him not to pay it,
emphatically declared that he owed Lovat nothing. He then went into
a long array of evidence, sufficient to have beheaded Lovat many
times over, as a traitor to the reigning family, and indeed no faithful
servant of the family desiring to reign. The traitor himself laughed
when this witness quoted a ballad in English, which Lovat had
composed, ‘in Erse’:—
When young Charley does come over,
There will be blows and blood good store.
‘When,’ said the witness, ‘I refused a commission offered me by the
Pretender, Lord Lovat told me I was guilty of High Treason.’ Further,
Lovat had drunk ‘Confusion to the White Horse and the whole
generation of them;’ and had cursed both the Reformation and the
Revolution. Lovat retorted by showing that this not disinterested
witness was a loyal man living at the expense of Government. ‘He is
trying to hang an old man to save himself,’ said Lovat. This was
warmly denied, but Lovat was right in the implication.
Lovat’s secretary, Fraser, was a dangerous FATHER AND
witness. He proved that, by Lord Lovat’s order, he, SON.
the secretary, wrote to Lord Loudon (in the service of
George II.) informing him that he was unable to keep his son out of
the rebellion, and another letter to the Pretender that, though unable
to go himself to help to restore the Stuarts, he had sent his eldest
son to their standard. It was shown that the son was disgusted at his
father’s double-dealing, and only yielded to him at last (in joining the
army of Charles Edward), on the ground that he was bound to obey
his sire and the chief of the clan Fraser. Undoubtedly, the attempt to
save himself by the sacrificing of his son, was the blackest spot in
Lovat’s mean, black, and cruel character. According to Walpole, ‘he
told’ Williamson, the Lieutenant of the Tower, ‘We will hang my eldest
son and then my second shall marry your niece!’
Fraser after Fraser gave adverse evidence. Lovat THE
maintained that they were compelled to speak against FRASERS.
him. One of them confessed, with much simplicity,
that he lived and boarded at a messenger’s house; but that he had
no orders to say what he had said. ‘I am free: I walk in the Park or
about Kensington; I go at night to take a glass,’—but he allowed that
the messenger went with him. One or two witnesses had very short
memories, or said what they could for their feudal superior. Another,
Walker, spoke to the anger of Lovat’s son, on being driven into
rebellion. ‘The Master of Lovat took his bonnet and threw it on the
floor. He threw the white cockade on the fire, and damned the
cockade, &c.’ Lord Lovat, on the other hand, had sworn he would
seize the cattle and plaids of all the Frasers who refused to rise, and
would burn their houses. One of these adverse Frasers, being hard
pressed by Lovat, allowed that he expected to escape punishment,
for his evidence, but that he had not been promised a pardon. ‘If,’
said he, ‘I give evidence, in any case it should be the truth; and,’ he
added, with a composure so comic that it might well have disturbed
the august solemnity, ‘if the truth were such as I should not care to
disclose, I would declare positively I would give no evidence at all.’
Another witness, a Lieutenant Campbell, in the king’s service, but
who had been a prisoner in the power of the Jacobites, being
questioned as to a conversation he had had with Lovat, made the
amusingly illogical remark, ‘As I did not expect to be called as a
witness, so I do not remember what passed on that occasion.’ The
lieutenant did, however, recollect one thing, namely, that Lovat had
said that his son had gone into the rebellion, but that he himself was
a very loyal person. A second officer, Sir Everard Falconer, secretary
to the Duke of Cumberland (and very recently married to Miss
Churchill, daughter of the old general), stated that he had been sent
by the duke to converse with Lovat, and he repeated the loyal
assertions that the prisoner had made. ‘Will your Lordship put any
question to Sir Everard?’ asked the Lord High Steward, of Lovat. ‘I
have only,’ replied Lovat, ‘to wish him joy of his young wife.’
 The most important witness of all was, of course,
MURRAY OF
Mr. Murray, of Boughton, late secretary to the young BOUGHTON.
Chevalier, and, only a day or two before, a prisoner in
the King’s Bench, from which he had been discharged. In the course
of his answers, Murray said he had been ‘directed’ to give a narrative
of the springs and progress of the late rebellion,—when he came to
be examined at the Bar of the High Court of Justice, where he was
then standing. ‘Directed?’ exclaimed the Earl of Cholmondely, ‘who
directed you?’ The Lord High Steward and the Earl of Chesterfield
protested they had not heard the word ‘directed’ used by the witness.
There was a wish to have the matter cleared up, and Murray then
said, ‘Some days after my examination in the Tower, by the
honourable Committee of the House of Commons, a gentleman,
who, I believe was their secretary, came to me to take a further
examination; and to ask me as to any other matter that had occurred
since my last examination. Some days after that, he told me I should
be called here before your Lordships, upon the trial of my Lord
Lovat, and that at the same time, it would be expected that I should
give an account of the rise and progress of the Rebellion in general.’
The above shows pretty clearly how the weak MURRAY’S
natures of prisoners in the Tower were dealt with, in EVIDENCE.
order to get evidence by which they would destroy at
once the life of a confederate and their own honour. Murray did what
he was ‘directed’ or ‘expected’ to do, without passion but with some
sense of pain and shame. The whole rise and course of the
insurrection may be found in his testimony; he was prepared for the
questions, equally so with the answers he gave to them; and his
evidence is of importance for a proper understanding of the
outbreak. Some merit was made of his ‘voluntary surrender,’ but
Lord Talbot, quite in Lovat’s interest, roughly asked if Murray had
really intended to surrender himself at the time he became a prisoner
to the Royal forces. The poor man truthfully answered that ‘it was not
then my intention particularly to surrender myself’;—adding, ‘it was
not my intention till I saw the dragoons;’—but that he had never
since attempted to escape.—‘Have you ever taken the Oaths of
Allegiance and Fidelity to the King?’ asked Lord Talbot. He never
had. ‘Did you ever take such Oaths to anybody else?’ Murray let
drop a murmured ‘No’; and then Sir William Yonge,
CROSS
one of the Managers for the Commons, came to his EXAMINATION.
help, with the expression of a hope that the king’s
witness should not be obliged to answer questions that tended to
accuse himself of High Treason. To which Lord Talbot replied that the
gentleman had already confessed himself guilty of that crime. Lord
Talbot then asked Murray if he was a voluntary evidence. Murray
requested him to explain what he meant by those two words. ‘Are
you here?’ said Talbot, ‘in hopes of a pardon? And if you had been
pardoned, would you now be here as a witness at all?’ The Attorney-
General came to the rescue. It was an improper question, he said,
resting upon the supposition of a fact which had not happened. Lord
Talbot insisted: he asked Murray, ‘Do you believe your life depends
upon the conformity of the evidence you shall give on this trial, with
former examinations which you have undergone?’ There was a fight
over this matter, but a lull came in the fray, and then Murray spoke
with a certain dignity, and said: ‘I am upon my oath and obliged to tell
the truth; and I say that possibly and very probably, had I been in
another situation of life, I should not have appeared before your
Lordships as a witness against the noble Lord at the Bar.’ There was
a touch of mournful sarcasm in Murray’s truthful answer, which
escaped Lord Talbot, for he remarked: ‘I am extremely well satisfied
with the gentleman’s answer; and it gives me a much better opinion
of his evidence than I had before.’
The conclusion of the protracted affair was that
THE VERDICT.
Lovat was pronounced guilty by the unanimous
verdict of 117 peers. He made no defence by which he could profit;
and when he spoke in arrest of judgment, he said little to the
purpose. There was a sorry sort of humour in one or two of his
remarks. He had suffered in this trial by two Murrays, he said, by the
bitter evidence of one, and the fatal eloquence of another, by which
he was hurried into eternity. Nevertheless, though the eloquence had
been employed against him, he had listened to it with pleasure. ‘I
had great need of my friend Murray’s eloquence for half an hour,
myself; then, it would have been altogether agreeable to me!’ In
whatever he himself had done, there was, he said, really no
malicious intention. If he had not been ill-used by the Government in
London, there would have been no rebellion in the Frasers’ country.
George I. had been his ‘dear master;’ for George II. he had the
greatest respect. He hoped the Lords would intercede to procure for
him the royal mercy. The Commons had been severe against him, let
them now be merciful. Nothing of this availed Lovat. The peevish
Lord Hardwicke called him to order; and then, with a calm
satisfaction, pronounced the horrible sentence which told a traitor
how he should die. Lovat put a good face on this bad matter.—‘God
bless you all!’ he said, ‘I bid you an everlasting farewell.’ And then,
with a grim humour, he remarked:—‘We shall not meet all in the
same place again, I am quite sure of that!’ He afterwards desired, if
he must die, that it should be in the old style of the Scottish nobility,
—by the Maiden.
While this tragic drama was in progress, there
GENTLEMAN
arose a report in the coffee-houses of a Jacobite plot. HARRY.
It came in this way. At the March sessions of the Old
Bailey, a young highwayman, named Henry Simms, was the only
offender who was capitally convicted. ‘If it hadn’t been for me,’ said
the handsome highwayman, ‘you would have had a kind of maiden
assize; so, you might as well let me go!’ As the judges differed from
him, he pointed to some dear friends in the body of the court, and
remarked, ‘Here are half a dozen of gentlemen who deserve hanging
quite as much as I do.’ The Bench did not doubt it, but the remark
did not profit Gentleman Harry, himself, as the young women and
aspiring boys on the suburban roads called him. But Mr. Simms was
a man of resources. As he sat over his punch in Newgate, he
bethought himself of a means of escape. He knew, he said, of a
hellish Jacobite plot to murder the king and upset the Happy
Establishment. Grave ministers went down to Newgate and listened
to information which was directed against several eminent persons.
Harry, however, lacked the genius of Titus Oates; and besides, the
people in power were not in want of a plot; the information would not
‘hold water.’ The usual countless mob of savages saw him ‘go off’ at
Tyburn; and then eagerly looked forward to the expected grander
display on Tower Hill. But Lovat and his friends spared no pains to
postpone that display altogether.
 The Scots made a national question of it. The Duke of Argyle
especially exerted himself to get the sentence commuted for one of
perpetual imprisonment. This was accounted for by Mr. Harris
(Malmesbury Correspondence), in the following manner: ‘The Duke
owes Lord Lovat a good turn for letting the world know how active
his Grace was in serving the Government in 1715, and for some
panegyric which the Duke is not a little pleased with.’
In the Tower, Lovat mingled seriousness and buffoonery together.
But this was natural to him. There was no excitement about him, nor
affectation. He naturally talked much about himself; but he had
leisure and self-possession to converse with his visitors on other
topics besides himself. Only two or three days before his execution
he was talking with two Scottish landed proprietors. The subject was
the Jurisdiction Bill. ‘You ought to be against the Bill,’ said Lovat; ‘the
increase of your estates by that Bill will not give you such an interest
at Court as the power did which you are thereby to be deprived of.’
The interest of his own friends at Court was gone.
On April the 2nd, the Sheriffs of London received THE DEATH
the ‘death warrant’ from the Duke of Newcastle for WARRANT.
Lovat’s execution. At the same time, a verbal
message was sent expressing the duke’s expectation that the
decapitated head should be held up, and denounced as that of a
traitor, at the four corners of the scaffold.
On the 9th, the hour had come and the old man EXECUTION.
was there to meet it. It is due to him to say that he
died like a man, therein exemplifying a remark made by Sir Dudley
Carleton, on a similar occurrence, ‘So much easier is it for a man to
die well than to live well.’ Lovat was very long over his toilet, from
infirm habit, and he complained of the pain and trouble it gave him to
hobble down the steps from his room, in order to have his head
struck off his shoulders. On the scaffold, he gazed round him and
wondered at the thousands who had assembled to see such a
melancholy sight. He quoted Latin lines, as if they illustrated a
patriotism or virtue which he had never possessed or practised. He
would have touched the edge of the axe, but the headsman would
not consent till the Sheriffs gave their sanction. With, or apart from all
this, ‘he died,’ says Walpole, ‘without passion, affectation,
buffoonery, or timidity. His behaviour was natural and intrepid.’
Walpole adds, ‘He professed himself a Jansenist.’ Other accounts
say, ‘a Papist,’ which is a Jansenist and something more. ‘He made
no speech; but sat down a little while in a chair on the scaffold, and
talked to the people round him. He said, he was glad to suffer for his
country, dulce est pro patriâ mori; that he did not know how, but that
he had always loved it, Nescio quâ natale solum, &c.; that he had
never swerved from his principles, (!) and that this was the character
of his family who had been gentlemen for 500 years! He lay down
quietly, gave the sign soon, and was despatched at a blow. I believe
it will strike some terror into the Highlands, when they hear there is
any power great enough to bring so potent a tyrant to the block. A
scaffold fell down and killed several persons; one, a man that had
ridden post from Salisbury the day before to see the ceremony; and
a woman was taken up dead with a live child in her arms.’ This
scaffold consisted of several tiers which were occupied by at least a
thousand spectators. It was built out from the Ship, at the corner of
Barking alley. About a dozen people were killed at the first crash,
which also wounded many who died in hospital. The master-
carpenter who erected it, had so little thought of its instability, that he
established a bar and tap beneath it. He was joyously serving out
liquors to as joyous customers, when down came the fabric and
overwhelmed them all. The carpenter was among the killed.
The head was not held up nor its late owner GEORGE
denounced as a traitor. The Duke of Newcastle was SELWYN.
displeased at the omission, but the Sheriffs justified
themselves on the ground that the custom had not been observed at
the execution of Lord Balmerino, and that the duke had not
authorised them to act, in writing. A sample of the levity of the time is
furnished in the accounts of the crowds that flocked to the trial as
they might have done to some gay spectacle; and an example of its
callousness may be found in what Walpole calls, ‘an excessive good
story of George Selwyn.’ ‘Some women were scolding him for going
to see the execution, and asked him how he could be such a
barbarian to see the head cut off?’ “Nay,” says he, “if that be such a
crime, I am sure I have made amends, for I went to see it sewed on
again!” When he was at the undertaker’s, Stephenson’s in the
Strand, as soon as they had stitched him together, and were going to
put the body into the coffin, George, in my Lord Chancellor’s voice,
said, “My Lord Lovat, your Lordship may rise.”’
Lovat had expressed a passionate desire to be
LOVAT’S
buried in his native country, under the shadow of its BODY.
hills, his clansmen paying the last duty to their chief,
and the women of the tribe keening their death-song on the way to
the grave. The Duke of Newcastle consented. The evening before
the day appointed for leaving the Tower, a coachman drove a hearse
about the court of the prison, ‘before my Lord Traquair’s dungeon,’
says Walpole, ‘which could be no agreeable sight, it might to Lord
Cromartie, who is above the chair.’ Walpole treats Lord Traquair with
the most scathing contempt, as if he were both coward and traitor,
ready to purchase life at any cost. After all, Lovat’s body never left
the Tower. ‘The Duke of Newcastle,’ writes Walpole to Conway, 16th
April, on which night London was all sky-rockets and bonfires for last
year’s victory, ‘has burst ten yards of breeches-strings, about the
body, which was to be sent into Scotland; but it seems it is
customary for vast numbers to rise, to attend the most trivial burial.
The Duke, who is always at least as much frightened at doing right
as at doing wrong, was three days before he got courage enough to
order the burying in the Tower.’
Lovat’s trial brought about a change in the law. On the 5th of May,
Sir William Yonge, in the House of Commons, brought in a good-
natured Bill, without opposition, ‘to allow council to prisoners on
impeachment for treason, as they have on indictments. It hurt
everybody at old Lovat’s trial, all guilty as he was, to see an old
wretch worried by the first lawyers in England, without any
assistance, but his own unpractised defence. This was a point
struggled for in King William’s reign, as a privilege and dignity
inherent in the Commons—that the accused by them should have no
assistance of council. How reasonable that men chosen by their
fellow-subjects for the defence of their fellow-subjects should have
rights detrimental to the good of the people whom they are to
protect. Thank God! we are a better-natured age, and have
relinquished this savage principle with a good grace.’ So wrote
Walpole in Arlington Street.
After Lovat’s death, the friends of the Happy Establishment
ceased to have fears for the stability of the happiness or for that of
the establishment. Walpole declined thenceforth to entertain any
idea of Pretender, young or old, unless either of them got south of
Derby. When Charles Edward ‘could not get to London with all the
advantages which the ministry had smoothed for him, how could he
ever meet more concurring circumstances?’ Meanwhile, the ‘Duke’s
Head,’ as a sign, had taken place of Admiral Vernon’s in and about
the metropolis, as Vernon’s had of the illustrious Jacobite’s—the
Duke of Ormond.
There was in Piccadilly an inn, whose loyal host, THE WHITE
Williams, had set up the then very loyal sign of ‘The HORSE,
White Horse’ (of Hanover). While Lovat’s trial was PICCADILLY.
proceeding, that Whig Boniface had reason to know
that the Jacobites were not so thoroughly stamped out as they
seemed to be. Williams attended an anniversary dinner of the
Electors of Westminster, who supported ‘the good old cause.’ He
was observed to be taking notes of the toasts and speeches, and he
was severely beaten and ejected. He laid an information against this
Jacobite gathering, and he described one of the treasonable
practices thus:—‘On the King’s health being drunk, every man held a
glass of water in his left hand, and waved a glass of wine over it with
the right.’ A Committee of the House of Commons made so foolish
an affair of it as to be unable to draw up a ‘Report.’ If the enquiry had
extended three years back, Walpole thinks, ‘Lords Sandwich and
Grenville of the Admiralty would have made an admirable figure as
dictators of some of the most Jacobite toasts that ever were
invented. Lord Donerail ... plagued Lyttelton to death with pressing
him to enquire into the healths of the year ’43.’
On the first anniversary of Culloden, the JACOBITE
celebration of the day was as universally joyous as TOASTS.
when the news of the victory first reached town. The
papers speak of a ‘numerous and splendid appearance of nobility,’ at
St. James’s; of foreign ministers and native gentry, eager to pay their
compliments to his Majesty on this occasion. At night, London was in
a blaze of bonfires and illuminations. At the same time, in houses
where Jacobites met, they drank the very enigmatical toast, ‘The
three W’s,’ and talked of a private manifesto of the Chevalier to his
faithful supporters, which stated that the late attempt was an essay,
which would be followed in due time by an expedition made with an
irresistible force. But there were also Jacobites who ‘mourned
Fifteen renewed in Forty-five,’ and whose sentiments were
subsequently expressed by Churchill’s Jockey in the ‘Prophecy of
Famine’:—
Full sorely may we all lament that day,
For all were losers in the deadly fray.
Five brothers had I on the Scottish plains,
Well do’st thou know were none more hopeful swains:
Five brothers there I lost in manhood’s pride;
Two in the field, and three on gibbets died.
Ah! silly swains to follow war’s alarms;
Ah, what hath shepherd life to do with arms?
There was still an untried rebel peer in the Tower, THE EARL OF
the Earl of Traquair. He bore the royal name of TRAQUAIR.
Charles Stuart, and had some drops of the Stuart blood in his veins.
Captured in 1746, he had seen the arrival of Lovat at, and also his
departure from, the Tower. Soon after the latter event, there was
some talk of impeaching the earl; but this was held to be idle talk
when the earl was seen enjoying the liberty of the Tower—walking in
one of the courts with his friends. Whether he had rendered any
service to Government, to be deserving of this favour and
subsequent immunity, is not known. Walpole, when Lovat’s trial was
going on, said, ‘It is much expected that Lord Traquair, who is a great
coward, will give ample information of the whole plot.’ However, it is
certain that many Jacobites were pardoned without any such
baseness being exacted from them. Sir Hector Maclean and half-a-
dozen other semi-liberated rebels were to be seen going about
London, with a messenger attending on them. Other messengers,
however, were often sudden and unwelcome visitors in private
houses, in search for treasonable papers and traitorous persons.
Gentleman Harry’s idea of a plot was said, in loyal coffee-houses, to
be a reality; and the quidnuncs there were quite sure that money
was going into the Highlands from France, and small bodies of
Frenchmen were also being sent thither, and capable Scottish and
English sergeants were now and then disappearing. The only
ostensible steps taken by the Government was to make a new army-
regulation, namely, that the 3rd (Scottish) regiment of Foot Guards,
and all other regiments, bearing the name Scottish, should
henceforward be called English, and ‘the drums to beat none but
English marches.’
Therewith came a doubtful sort of pardoning to PLOTTING
about a thousand rebels cooped up in vessels on the AND
Thames, or in prisons ashore. They, and some PARDONING.
Southwark prisoners who had been condemned to
death, were compelled to suffer transportation to the American
Plantations. ‘They will be transported for life,’ the papers tell their
readers, ‘let them be of what quality and condition soever.’
There was one Jacobite prisoner in Newgate who ÆNEAS
was disinclined to live in durance, to take his trial, or MACDONALD.
to be hanged after it or transported without it. This
was Æneas or Angus Macdonald, known as the Pretender’s Banker.
He had surrendered soon after Culloden, and was lodged in
Newgate. Seeing the death-like aspect of things, Macdonald got two
friends to call upon him, one evening. There was nothing strange in
such a visit. Newgate was like a huge hotel, open at all hours, where
turnkeys acted as footmen who introduced visitors. Young Mr.
Ackerman, the keeper’s son, received Mr. Macdonald’s friends. As
soon as he had opened the wicket, behind which the prisoner was
standing, they knocked Ackerman down, and as he was attempting
to rise, they flung handfuls of snuff into his face. He succeeded in
getting on his legs, but, when he could open his eyes, the captive
and his friends had disappeared. Alarm was given; young Ackerman
led the pursuit, and he came up with Macdonald in an adjacent
street. Æneas faced his pursuer as if to quietly surrender, but as
soon as Ackerman came near, he flung a cloud of snuff into his face.
The gaoler struck him down with his keys and broke his collarbone.
When Macdonald was again within the prison walls, he politely
apologised for the trouble he had given. Mr. Ackerman quite as
politely begged him not to think of it, ‘but, you see, Sir,’ he added, ‘I
am bound to take care it does not happen again,’ and clapping a
heavy suit of irons on the prisoner’s limbs, he stapled and screwed
the banker down to the floor, sending the surgeon to him to look to
his collarbone.
The banker’s trial was put off from time to time, THE
between July and December. The public in general COUNTESS
were beginning to doubt its ever coming on at all; and OF
the autumn seemed dull to people now long used to DERWENTWAT
ER.
excitement, when London suddenly heard that
Charles Radcliffe’s widow, with a son and two daughters, had arrived
in London, and had taken a mansion in, then highly fashionable,
Golden Square. She was a Countess (of Newburgh), in her own
right; but, of course, the gentry with Jacobite sympathies, who called
on her, recognised her as Countess of Derwentwater. This arrival in
Golden Square may have had some influence on a demonstration at
Westminster Abbey. For years, on the anniversary of that rather un-
English king and canonized saint, Edward the Confessor, groups of
Roman Catholics were accustomed to gather round his shrine,
kneeling in prayer. ‘Last Tuesday,’ says the ‘Penny Post,’ ‘being the
anniversary of Edward the Confessor, the tombs were shut in
Westminster Abbey, by order of the Dean and Chapter, to prevent
the great concourse of Roman Catholics, who always repair there on
that day. Notwithstanding which, most of them were kneeling all the
day at the gates, paying their devotions to that Saint.’
This incident having passed out of discussion, the trial of
Macdonald was looked for. When it did come on, in December, at St.
Margaret’s, Southwark, it disappointed the amateurs of executions,
and delighted the Jacobites. The prisoner’s main plea was that he
was French, and was legally at Culloden. The jury found that he was
not French, but was a Scotch rebel. He was sentenced to death; but
the whole thing was a solemn farce, the sentence was not carried
out; and we shall presently see wherefore he was immediately