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Electronic and
Optical Properties of
raphite-Related Systems
G
Electronic and
Optical Properties of
raphite-Related Systems
G
By
Chiun-Yan Lin
Department of Physics, National Cheng Kung University, Taiwan
Rong-Bin Chen
Center of General Studies, National Kaohsiung Marine University, Taiwan
Yen-Hung Ho
Department of Physics, National Tsing Hua University, Taiwan
Ming-Fa Lin
Department of Physics, National Cheng Kung University, Taiwan
CRC Press
Taylor & Francis Group
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© 2018 by Taylor & Francis Group, LLC
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Contents
Preface..................................................................................................................... vii
Authors.....................................................................................................................ix
1 Introduction......................................................................................................1
2 Theoretical Models and Experimental Techniques.................................9

2.1 Magnetic Tight-Binding Model for Layered Graphites.................... 9
2.1.1 Simple Hexagonal Graphite.................................................. 12
2.1.2 Bernal Graphite....................................................................... 13
2.1.3 Rhombohedral Graphite........................................................ 15
2.1.4 Gradient Approximation for Optical Properties................ 18
2.2 Scanning Tunneling Microscopy and Spectroscopy......................22
2.3 Angle-Resolved Photoemission Spectroscopy................................ 24
2.4 Absorption Spectroscopy.................................................................... 25
3 Simple Hexagonal Graphite........................................................................ 29

3.1 Electronic Structures without External Fields................................. 29
3.2 Optical Properties without External Fields......................................34
3.3 Magnetic Quantization....................................................................... 36
3.3.1 Landau Levels and Wave Functions.................................... 36
3.3.2 Landau-Subband Energy Spectra......................................... 38
3.4 Magneto-Optical Properties...............................................................43
4 Bernal Graphite.............................................................................................. 51
4.2 Optical Properties without External Fields......................................54
4.3 Magnetic Quantization....................................................................... 57
4.3.1 Landau Subbands and Wave Functions.............................. 57
4.3.2 Anti-Crossings of Landau Subbands................................... 60
4.4 Magneto-Optical Properties............................................................... 62
5 Rhombohedral Graphite.............................................................................. 69
5.2 Anisotropic Dirac Cone Along a Nodal Spiral................................ 71
5.3 Dimensional Crossover....................................................................... 73
5.4 Optical Properties without External Fields...................................... 75
5.5 Magneto-Electronic Properties.......................................................... 76
5.5.1 Tight-Binding Model.............................................................. 76
5.5.2 Onsager Quantization............................................................ 78
5.6 Magneto-Optical Properties............................................................... 82
v
vi Contents
6 Quantum Confinement in Carbon Nanotubes and

Graphene Nanoribbons ...............................................................................85
6.1 Magneto-Electronic Properties of Carbon Nanotubes .................. 85
6.2 Magneto-Optical Spectra of Carbon Nanotubes............................. 91
6.3 Magneto-Electronic Properties of Graphene Nanoribbons........... 96
6.4 Magneto-Optical Spectra of Graphene Nanoribbons..................... 99
6.5 Comparisons and Applications....................................................... 107
7 Concluding Remarks.................................................................................. 113
Problems............................................................................................................... 121
References............................................................................................................ 123
Index...................................................................................................................... 147
Preface
This book is intended as an introduction to the electronic and optical

properties of graphite-related systems. A systematic review is made for
AA-, AB- and ABC-stacked graphites. The generalized tight-binding model,
accompanied by the effective-mass approximation and the Kubo formula, is
developed to investigate electronic and optical properties in the presence/
absence of a uniform magnetic field. The unusual electronic properties cover
the stacking-dependent Dirac-cone structures, the significant energy widths
along the stacking direction, the Landau subbands crossing the Fermi level,
the magnetic-field-dependent Landau-subband energy spectra with cross-
ings and anti-crossings, and the monolayer- or bilayer-like Landau wave
functions. There are configuration-created special structures in density of
states and optical spectra. The three kinds of graphites are quite different
from one another in terms of the available inter-Landau-subband excita-
tion channels, including the number, frequency, intensity and structure of
absorption peaks. The dimensional crossover presents the main similarities
and differences between graphites and graphenes; furthermore, the quan-
tum confinement enriches the magnetic quantization phenomena in carbon
nanotubes and graphene nanoribbons. The cooperative/competitive relations
between the interlayer atomic interactions, dimensions and magnetic quan-
tization are responsible for the diversified essential properties. Some of the
theoretical predictions are consistent with the experimental measurements.
Chiun-Yan Lin, Rong-Bin Chen,

Yen-Hung Ho, and Ming-Fa Lin
vii
Authors
Rong-Bin Chen is a professor at the Center of General

Studies, National Kaohsiung Marine University, Taiwan.
He received his PhD degree in physics from the University
of Cheng Kung in 2000 studying III-V semiconductor
physics. His main research interests are condensed mat-
ter theory; electronic and optical properties of graphene,
low-dimensional materials, and carbon-related systems.
Yen-Hung Ho received his PhD in physics in 2009 from

the National Cheng-Kung University, Taiwan. Currently,
he is a postdoctoral researcher at the National Center
for Theoretical Sciences and Physics Department in
National Tsing-Hua University. His research mainly
focuses on the model calculations of electronic proper-
ties for nanomaterials in response to external magnetic,
electric and strain fields.
Chiun-Yan Lin obtained his PhD in 2014 in physics from

the National Cheng Kung University (NCKU), Taiwan.
Since 2014, he has been a postdoctoral researcher in the
department of physics at NCKU. His main scientific
interests are in the field of condensed matter physics,
modeling and simulation of nanomaterials. Most of his
research is focused on the electronic and optical proper-
ties of two dimensional nanomaterials.
Ming-Fa Lin is a distinguished professor in the

Department of Physics, National Cheng Kung University,
Taiwan. He received his PhD in physics in 1993 from the
National Tsing-Hua University, Taiwan. His main sci-
entific interests focus on essential properties of carbon
related materials and low-dimensional systems.
ix
1
Introduction
Carbon atoms can form various condensed-matter systems with unique

geometric structures, mainly owing to four active atomic orbitals. Zero-
to three-dimensional carbon-related systems cover diamond [1], graphite
[2–4], graphene [5], graphene nanoribbons [6], carbon nanotubes [7] and car-
bon fullerene [8]. All of these have sp2 bonding except for diamond which
has sp3. The former might exhibit similar physical properties, for example,
π-electronic optical excitations [9,10]. Graphite is one of the most extensively
studied materials, theoretically and experimentally. This layered system is
very suitable for exploring diverse 3D and 2D phenomena. The interplane
attractive forces originate from the weak Van der Waals interactions of
the 2pz orbitals. The honeycomb lattice and the stacking configuration are
responsible for the unique properties of graphite, for example, its semime-
tallic behavior due to the hexagonal symmetry and the interlayer atomic
interactions. The essential properties are dramatically changed by the inter-
calation of various atoms and molecules. Graphite intercalation compounds
can achieve a conductivity as good as copper [4,11–13]. In general, there exist
three kinds of ordered configurations in the layered graphites and com-
pounds, namely AA, AB and ABC stackings. Simple hexagonal (AA), Bernal
(AB) and rhombohedral graphites (ABC) exhibit rich and diverse electronic
and optical properties in the presence/absence of a uniform magnetic field
(B = B0 zˆ ). To present a systematic review of them, the generalized tight-bind-
ing model is developed under magnetic quantization. This model, combined
with the Kubo formula, is utilized to investigate the essential properties of
layered carbon-related systems. The dimensional crossover from graphene
to graphite and the quantum confinement in nanotube and nanoribbon sys-
tems are discussed thoroughly. A detailed comparison with other theoretical
studies and experimental measurements is also made.
Few-layer and multilayer graphenes, with distinct stacking configurations,
have been successfully produced using various experimental methods since
the first discovery of monolayer graphene in 2004 by mechanical exfoliation
[5]. They possess a hexagonal symmetry and a nanoscale size, leading to
many remarkable characteristics, for example, they have the largest Young’s
modulus [15], feature-rich energy bands [16,17], diverse optical selective rules
[18–25], unique magnetic quantization [27–36], anomalous quantum Hall
effects (QHE) [37–41] and multimode plasmons [42–45]. Their electronic and
optical properties are very sensitive to changes to the stacking configuration
[16,29,31,33,34,36], layer number [16,29,31,36], magnetic field [17–24,27–32,36],
1
2 Electronic and Optical Properties of Graphite-Related Systems
electric field [17,32], mechanical strain [16,17], doping [16,17] and sliding [35].
Five kinds of electronic structures—linear [36], parabolic [27,31,36], partially
flat [31,36], sombrero-shaped [31,32,36] and oscillatory [32,34,35] energy
bands—are revealed in AB- and ABC-stacking systems. Oscillatory bands
can be created by a perpendicular electric field. However, the AA stacking
only has the first kind of electronic structure. Specifically, the intersection of
the linear valence and conduction bands can form the so-called Dirac-cone
structure. The main features of energy bands are directly reflected in the
other essential properties. The finite-layer confinement effects are expected
to induce important differences between the layered graphenes and graph-
ites. The close relations arising from the dimensional crossover deserve a
thorough investigation.
Graphite crystals are made up of a series of stacked graphene planes.
Among three kinds of ordered stacking configurations, AB-stacked graphite
is predicted to have the lowest ground state energy according to the first-
principles calculations [46]. Natural graphite presents dominant AB stacking
and partial ABC stacking [2,3]. AA-stacked graphite, which possesses the
simplest crystal structure, does not exist naturally. The periodical AA stack-
ing is first observed in the Li-intercalation graphite compounds [4] with a
high free electron density and a super conducting transition temperature of
1.9 K [14]. Simple hexagonal graphite is successfully synthesized by using DC
plasma in hydrogen-methane mixtures [47], and AA-stacked graphenes are
generated using the method of Hummers and Offeman and chemical-vapor
deposition (CVD) [48,49]. Furthermore, the AA-stacking sequence is con-
firmed through high-resolution transmission electron microscopy (HRTEM)
[48]. Specifically, angle-resolved photoemission spectroscopy (ARPES), a
powerful tool in the direct identification of energy bands, is utilized to exam-
ine two/three pairs of Dirac-cone structures in AA-stacked bilayers/trilayers
[50,51].
AA-stacking systems have stirred many theoretical research studies, such
as the investigation of band structures [29,31,52,53,53], magnetic quantization
[29,31,36,54,55], optical properties [56–58], Coulomb excitations [59,61–63],
quantum transport [66] and phonon spectra [67]. Simple hexagonal graphite,
a 3D-layered system with the same graphitic sheets on the (x, y)-plane, was
first proposed by Charlier et al. [46]. From the tight-binding model and the
first-principles method, this system belongs to a band-overlap semimetal,
in which the same electron and hole density originate from the significant
interlayer atomic interactions. There is one pair of low-lying valence and con-
duction bands. The critical feature is the vertical Dirac-cone structure with a
sufficiently wide bandwidth of ~ 1 eV along the kz-direction (k wave vector).
Similarly, the AA-stacked graphene is predicted to exhibit multiple Dirac
cones vertical to one another [29,36,52]. Moreover, Bloch wave functions are
the only symmetric or anti-symmetric superpositions of the tight-binding
functions on the distinct sublattices and layers [36]. Apparently, these 3D
and 2D vertical Dirac cones will dominate the other low-energy essential
Introduction 3
properties, for example, the special structures in density of states (DOS)

[36,53,54], the quantized Landau subbands (LSs) and levels (LLs) [29,36,55], the
rich optical spectra [57,58] and the diversified plasmon modes [59,61–63]. The
magnetic quantization is frequently explored by the effective-mass approxi-
mation [29] and the generalized tight-binding model [31,36]. It is initiated
from the vertical Dirac points: the extreme points in the energy‑wave‑vector
space. This creates the specific B0-dependent energy spectra and the well-
behaved charge distributions, thus leading to the diverse and unique mag-
neto-absorption peaks, for example, the intraband and interband inter-LS
excitations, the multichannel threshold peaks and the beating-form absorp-
tion peaks in AA-stacked graphite [55,57,58]. The predicted band structures,
energy spectra and optical excitations can be verified by ARPES [50,51], scan-
ning tunneling spectroscopy (STS) [64,65] and optical spectroscopy [20–24],
respectively.
Bernal graphite is a well-known semimetal [2] with a conduction electron
concentration of ~5 × 1018/cm3. Furthermore, the AB-stacking configuration
is frequently observed in the layered systems, for example, bilayer [5,68],
trilayer [68–70] and tetralayer graphenes [68]. AB-stacked graphite possesses
two pairs of low-lying energy bands that are dominated by the 2pz orbitals,
owing to a primitive unit cell with two neighboring layers. The highly aniso-
tropic band structure, the strong and weak energy dispersions along the (kx,
ky) plane and kz-axis, respectively, is confirmed by the ARPES measurements
[71–75]. Similar examinations are done for two pairs of parabolic bands in a
bilayer AB stacking [78,79], and the linear and parabolic bands in a trilayer
system [78,80]. The measured DOS of Bernal graphite presents the splitting π
and π* peaks at the middle energy (approximately 0.5eV–0.8eV) [64], reflecting
the highly accumulated states near the saddle points. Furthermore, it is finite
near the Fermi level (Ef ) because of the semimetallic behavior [65]. An elec-
tric-field-induced band gap is observed in the bilayer AB stacking [69]. The
magnetically quantized energy spectra, with many special structures, are
also identified using the STS measurements for AB-stacked graphite [81,82]
and graphenes [83,84], especially the square-root and linear dependences
on the magnetic field strength (the monolayer- and bilayer-like behaviors at
low energy). From the optical measurements, Bernal graphite shows a very
prominent π-electronic absorption peak at frequency ~5 eV [85], as revealed in
carbon-related systems with the sp2 bonding [86,87]. Concerning the low-fre-
quency magneto-optical experiments, the measured excitation spectra due to
LSs [88–92,94,96] or LLs [18–24] clearly reveal a lot of pronounced absorption
structures, the selection rule of ∆n = ±1 (n quantum number) and the strong
dependence on the wave vector of kz or the layer number (N).
The earliest attempt to calculate the band structures of monolayer gra-
phene and Bernal graphite was made by Wallace using the tight-binding
model with the atomic interactions of 2pz orbitals [97]. The former 2D sys-
tem has the linear valence and conduction bands intersecting at EF, where it
belongs to a zero-gap semiconductor with a vanishing DOS. However, the
semimetallic, 3D electronic structure can be further comprehended through

the Slonczewski–Weiss–McClure Hamiltonian involving important intra-
layer and interlayer atomic interactions [98,99]. The magnetic Hamiltonian
can be solved by the low-energy perturbation approximation, in which the
LS energy spectra exhibit crossing and anti-crossing behaviors [101,102]. The
generalized tight-binding model, which deals with the magnetic field and
all atomic interactions simultaneously, was developed to explore the main
features of LSs, for example, two groups of valence and conduction LSs, and
the layer-, kz- and B0-dependent spatial oscillation modes [88,100]. As to the
AB-stacked graphenes, their electronic and magneto-electronic properties
present bilayer- and monolayer-like behaviors, which are associated with
two pairs of parabolic bands and a slightly distorted Dirac cone, respectively
[16,36]. The former is only revealed in the odd-N systems. Optical spectra of
AB-stacked systems are predicted to exhibit a strong dependence of special
structures on the layer number and dimension [18–24]. The magneto-optical
excitations arising from two groups of LSs in graphite or N groups of LLs
in graphenes could be evaluated using the generalized tight-binding model
[88]. On the other hand, those due to the first group of LSs/LLs are frequently
investigated in detail by the effective-mass approximation [101,102]. The cal-
culated electronic and optical properties are in agreement with the experi-
mental measurements [81,82].
The rhombohedral phase is usually found to be mixed with the Bernal
phase in natural graphite. The ABC-stacking sequence in bulk graphite is
directly identified from the experimental measurements of HRTEM [103],
x-ray diffraction [104–106] and scanning tunneling microscopy (STM)
[107,108]. Specifically, this stacking configuration can account for the mea-
sured 3D QHE with multiple plateau structures [109] as rhombohedral graph-
ite possesses well-separated LS energy spectra [111,112]. In addition, doped
Bernal graphite is predicted to exhibit only one plateau [113]. Both ABC- and
AB-stacked graphenes can be produced by the mechanical exfoliation of
kish graphite [114,115], CVD [116–119], chemical and electrochemical reduc-
tion of graphite oxide [120–122], arc discharge [123–125], flame synthesis [126]
and electrostatic manipulation of STM [127,130]. The ARPES measurements
have verified the partially flat, sombrero-shaped and linear bands in trilayer
ABC‑stacking [80]. As to the STS spectra, a pronounced peak at the Fermi
level characteristic of the partial flat band is revealed in trilayer and penta-
layer ABC stacking [128–130]. Moreover, infrared reflection spectroscopy and
absorption spectroscopy are utilized to examine the low-frequency optical
properties, displaying clear evidence of two-featured absorption structures
due to the partially flat and sombrero-shaped energy bands [131]. According
to the specific infrared conductivities, infrared scattering scanning near-
field optical microscopy can distinguish the ABC-stacking domains with
nanoscaled resolution from other domains. However, the magneto-optical
measurements for ABC-stacked graphenes have been absent up to now.
Introduction 5
ABC-stacked graphite has a rhombohedral unit cell, while AA- and

AB-stacked systems possess hexagonal ones. This critical difference in stack-
ing symmetry is responsible for the diversified essential properties. Among
three kinds of bulk graphites, rhombohedral graphite is expected to present
the smallest band overlap (the lowest free carrier density), and the weakest
energy dispersion along the kz-direction [110,132]. There also exists a robust
low-energy electronic structure: a 3D spiral Dirac-cone structure. This
results in unusual magnetic quantization [111,112,134], in which the quan-
tized LSs exhibit monolayer-like behavior and significant kz-dependence.
Previous studies show that four kinds of energy dispersions exist in ABC-
stacked graphenes [31,36]. Specifically, the partially flat bands corresponding
to the surface states and the sombrero-shaped bands are absent in the bulk
system. They can create diverse and unique LLs with asymmetric energy
spectra around EF, normal and abnormal B0-dependences, well-behaved and
distorted probability distributions, and frequent crossings and anti-cross-
ings [31,36]. Apparently, optical and magneto-optical properties are greatly
enriched by the layer number and dimension [135–138]. The quantized LLs
of the partially flat bands and the lowest sombrero-shaped band have been
verified by magneto-Raman spectroscopy for a large ABC domain in a gra-
phene multilayer flake [139]. Layered graphenes are predicted to have more
complicated excitation spectra compared with 3D systems. The former and
the latter, respectively, reveal N2 categories of inter-LL transitions and one
category of inter-LS excitations [136,137].
In addition to the stacking configurations, the distinct dimensions can cre-
ate diverse phenomena in carbon-related systems. Quantum confinement in
1D carbon nanotubes and graphene nanoribbons plays a critical role in the
essential properties. Systematic studies have been made for the former since
the successful synthesis of carbon nanotubes using arc-discharge evapora-
tion in 1991 [7]. Each carbon nanotube can be regarded as a rolled-up gra-
phene sheet in a cylindrical form. It is identified as a metal or semiconductor,
depending on the radius and chiral angle [140–142]. The geometry-depen-
dent energy spectra, with energy gaps (Eg’s), are directly verified from the
STS measurements [207,208]. Specifically, the cylindrical symmetry can pres-
ent the well-known Aharonov–Bohm effect under an axial magnetic field
[145–148]. This is confirmed by the experimental measurements on optical
[149,150] and transport properties [151–153]. However, a closed surface acts
as a high barrier in the formation of the dispersionless LLs, as a perpendicu-
lar magnetic field leads to a vanishing flux through carbon hexagons. It is
very difficult to observe the physical phenomena associated with the highly
degenerate states, except for very high field strength [154].
The essential properties are greatly enriched by the boundary conditions
in 1D systems. The open and periodical boundaries, which, respectively,
correspond to the graphene nanoribbon and carbon nanotube, induce the
important differences between them. A graphene nanoribbon is a finite-
width graphene or an unzipped carbon nanotube. Graphene nanoribbons
can be produced by cutting few-layer graphenes [155,156], unzipping mul-

tiwalled carbon nanotubes [157–159] and using direct chemical syntheses
[160–162]. The cooperative or competitive relations between the open bound-
ary, the edge structure and the magnetic field are responsible for the rich and
unique properties. The 1D parabolic bands, with energy gaps, in armchair
graphene nanoribbons are confirmed by ARPES [163]. Furthermore, STS has
verified the asymmetric DOS peaks and the finite-size effect on the energy
gap [164–167]. Optical spectra are predicted to have edge-dependent selec-
tion rules [168–170]. The theoretical calculations show that only quasi-LLs
(QLLs), with partially dispersionless relations, can survive in the presence of
a perpendicular magnetic field [171,172]. The magneto-optical selection rule,
as revealed in layered graphenes, sharply contrasts with that of the carbon
nanotubes with well-defined angular momenta along the azimuthal direc-
tion [173].
In this book, we propose and develop a generalized tight-binding model
to fully comprehend the electronic and optical properties of graphite-related
systems. The Hamiltonian is built from the tight-binding functions on the
distinct sublattices and layers, in which all important atomic interactions,
stacking configurations, layer numbers and external fields are taken into
account simultaneously. A rather large Hamiltonian matrix, being associated
with the periodical variation of the vector potential, is solved using an exact
diagonalization method. The essential properties can be evaluated very effi-
ciently. Moreover, the effective-mass approximation is utilized to provide the
qualitative behaviors and the semiquantitative results, for example, the layer-
dependent characteristics. Specifically, the Onsager quantization method is
introduced to study the magnetic LS energy spectra in ABC-stacked graphite
with unique spiral Dirac cones. Such approximations are useful in the identi-
fication of the critical atomic interactions that create the unusual properties.
The AA-, AB- and ABC-stacked graphites and graphenes, and 1D graphene
nanoribbons and carbon nanotubes, are worthy of a systematic review of
essential properties. Electronic and optical properties, which mainly come
from carbon 2pz orbitals, are investigated in the presence/absence of a mag-
netic field. Electronic structures, quantized LS and LL state energies, mag-
netic wave functions, DOS and optical spectral functions are included in the
calculated results. Band widths, energy dispersion relations, critical points
in energy-wave-vector space, crossings and anti-crossings of B0-dependent
energy spectra, spatial oscillation modes of localized probability distribu-
tions, and various special structures in DOS are explored in detail. The main
features of optical excitations focus on the available excitation channels; the
form, number, intensity and frequency of prominent absorption structures;
and the layer/dimension and field dependences. Moreover, the theoretical
predictions are compared with the ARPES, STS and optical measurements
and require more experimental examinations. Chapter 2 covers geometric
structures, important atomic interactions, the generalized tight-binding
model and the Kubo formula, in which the main issues are the construction
Introduction 7
of the magnetic Hamiltonian and the efficient combination of two meth-

ods. In Chapter 3, the stacking- and layer-enriched essential properties are
studied for the AA-stacked graphite and graphenes, especially those due
to multiple vertical Dirac-cone structures. The analytical band structures
and magneto-electronic energy spectra are obtained from the approximate
expansions around the high symmetry points. They illustrate the diversified
characteristics of the close relations between, for example, the determina-
tion of the close relations between the absorption spectra and the important
intralayer/interlayer atomic interactions. The dimensional crossover from
monolayer graphene to graphite creates the critical differences between 2D
and 3D phenomena, including the semiconductor–semimetal transition, the
kz-dependent band width, the LS/LL energy spectra near the Fermi level, the
optical gap and the low- and middle-frequency absorption structures.
The dramatic transformations of essential properties are clearly revealed in
distinct stacking configurations. As to the AB-stacked systems, the linear and
parabolic energy dispersions, crossings and anti-crossings of LS/LL energy
spectra, well-behaved and perturbed magnetic wave functions, layer- and
dimension-dependent optical spectra, and rich magneto-absorption peaks
are investigated in Chapter 4. The monolayer- and bilayer-like behaviors are
presented for Bernal graphite and layered AB stacking. Specifically, ABC-
stacked graphene has linear, parabolic, partially flat and sombrero-shaped
energy bands, while rhombohedral graphite exhibits a 3D spiral Dirac-cone
structure, as indicated in Chapter 5. Such characteristics are expected to cre-
ate unique essential properties. The low-energy approximation and magnetic
quantization are proposed to explain the diversified electronic properties and
optical spectra. In Chapter 6, the reduced dimension in graphene nanorib-
bons and carbon nanotubes leads to the rich essential properties being sensi-
tive to the open/periodical boundary condition, width/radius, edge/chiral
angle and external fields. Comparisons among the graphite-related systems
and potential applications are also discussed. Finally, Chapter 7 contains
concluding remarks and discusses how the theoretical framework could be
further extended to other mainstream layered materials.
2
Theoretical Models and
Experimental Techniques
In the presence of a uniform magnetic field, B = B0 zˆ, electrons are forced

to undergo cyclotron motion in the x–y plane. As a result, electronic states
are evolved into highly degenerate states, referred to as Landau subbands
(LSs) in graphites. The 1D LSs are calculated from the subenvelope func-
tions established on different sublattices in the framework of the general-
ized tight-binding model, which simultaneously takes into account external
fields and atomic interactions. The magneto-Hamiltonian is built from the
tight-binding functions coupled with a periodic Peierls phase in an enlarged
unit cell; the period depends on the commensurate relation between the lat-
tice constant and the Peierls phase. According to the Kubo formula, it could
be further utilized to comprehend the main features of magneto-absorption
spectra, which are closely related to the Landau-level spectrum and the tran-
sition matrix elements. The method provides accurate and reliable results for
a wide energy range. The three prototypical configurations of bulk graph-
ites, namely simple hexagonal, Bernal and rhombohedral graphites, are
chosen for a systematic review. The magnetic quantization in 3D graphene
systems shows interesting phenomena as a function of the stacking configu-
ration and the magnetic field strength. The aforementioned electronic and
optical properties can be experimentally verified by scanning tunneling
microscopy (STM), scanning tunneling spectroscopy (STS), angle-resolved
photoemission spectroscopy (ARPES) and absorption spectroscopy. A brief
introduction of these instruments will be presented.
2.1 Magnetic Tight-Binding Model for Layered Graphites

The geometric structures of simple hexagonal, Bernal and rhombohedral
bulk graphites are shown in Figure 2.1a through c. They are, respectively,
constructed from 2D graphene layers periodically stacked along ẑ with AA-,
AB- and ABC-stacking configurations, where the layer–layer distance Iz is
set as 3.35 Å. Detailed definitions of the stacking sequences are provided in
the following sections. The hexagonal unit cells of different graphites are
marked by the gray shadows, which contain two sublattices, Al and Bl, on
9
AA AB ABC
β2 β5
α2
α3 β3
γ3 γ4 β1 β4
γ1 γ5 γ2
α1
α0 γ0 β0
(a) (b) (c)
B
B1
A1 B2
A2 B2Rs–1
z A2Rs–1 B2Rs
y
A2Rs
x
(d)
A
H
Γ
k̂z L
K
M
k̂x k̂y
(e)
A
H
k̂z Γ
L
K
k̂x k̂y M
(f )
FIGURE 2.1
Geometric structures and atomic interactions of (a) AA-, (b) AB- and (c) ABC-stacked graphites;
(d) an enlarged unit cell in a magnetic field; (e) the zero-field first Brillouin zone; and (f) the
field-dependent reduced zone.
each layer, where l represents the number of the layer, and the symbols α,
β, and γ indicate the interlayer and intralayer hopping integrals. The first
Brillouin zone is a hexagonal prism, as shown in Figure 2.1e, where the
highly symmetric points are defined as Γ, M, K, A, L and H. The KH lengths
for the AA, AB and ABC stackings are, respectively, equal to π/Iz, π/2Iz and
π/3Iz based on the periods along ẑ.
Theoretical Models and Experimental Techniques 11
In general, the essential physical properties are mainly determined by 2pz

orbitals of carbon atoms. Built from the subspace spanned by the tight-bind-
ing functions ϕ Al and ϕ Bl (l = 1, 2, …), the wave function is characterized by
their linear combination over all A and B sublattices in a unit cell:
Ψ= ∑C
l
Al
ϕ A l + C Bl ϕ B l , (2.1)
where CAl and CBl are normalization factors. The tight-binding functions are
ϕ Al = ∑exp (ik ⋅ R ) χ (r − R )
R l
Al Al
A
(2.2)
ϕ Bl = ∑ (
RBl
exp ik ⋅ R Bl χ r − R Bl ,) ( )
where:
χ(r) is the atomic 2pz orbital of an isolated carbon
R is the position vector of an atom
The effective momentum in the presence of B is P − eA/c, so that the 3D

electronic bands of bulk graphites are quantized into the so-called 1D LSs.
R
A periodic Peierls phase GR ≡ 2π/φ0.
∫R′
A(r )dr is introduced to the tight-
binding functions in Equation 2.2, where A is the vector potential and
ϕ0 = 2πħc/e (4.1356 × 10−15 [T · m2]) is the flux quantum. The Hamiltonian ele-
ment coupled with the Peierls phase factor is given by
Ri
2π
i
φ0 ∫ A(r )⋅dr
i∆Gi , j
H B
i, j = Hi , je = Hi , je Rj
. (2.3)
The phase factor gives rise to an enlargement of the primitive unit cell
(Figure 2.1d), depending on the commensurate period of the lattice and the
Peierls phase. Using the Landau gauge A = (0, B0x, 0), the period of the phase
is l = 3RBbxˆ , in which there are 2RB A and 2RB B atoms in an enlarged unit

cell  RB =
( )
φ0 / 3 3 b′ 2 /2 79000 T 
.
 B0 B0 
This implies that the wave functions of graphites under a uniform mag-
netic field can be characterized by the subenvelope functions spanned over
all bases in the enlarged unit cell, the zero points of which are used to define
the quantum numbers of LSs. The wave function is decomposed into two
components in the magnetically enlarged unit cell as follows:
2 RB − 1 2 RB
Ψk = ∑ (A
m=1
o Amk + Bo Bmk ) + ∑ (A
m=1
e Amk + Be Bmk ), (2.4)
where o and e, respectively, represent the odd-indexed and even-indexed

parts. The subenvelope function Ao,e (Bo,e), described by an n-th order Hermite
polynomial multiplied with a Gaussian function, is an even or odd function
(depending on n) and represents the probability amplitude of the wave func-
tion contributed by each carbon atom. Considering the Peierls substitution
for interlayer and intralayer atomic interactions, we can obtain the explicit
form of the magnetic Hamiltonian matrix of bulk graphites. A procedure for
the band-like Hamiltonian matrix is further introduced to efficiently solve
the eigenvectors and eigenvalues by choosing an appropriate sequence
for the bases. In the following sections, the Hamiltonian matrices are derived
for simple hexagonal, Bernal and rhombohedral graphites in the generalized
tight-binding model.
2.1.1 Simple Hexagonal Graphite

In simple hexagonal graphite, each graphene sheet has the same projection on
the x−y plane, as shown in Figure 2.1a. The primitive unit cell includes only
two atoms that are the same as those of monolayer graphene. Four impor-
tant atomic interactions are used to describe the electronic properties, that is,
α0(= 2.569 eV), α1(= 0.361 eV), α2(= 0.013 eV) and α3(=−0.032 eV) [53], respectively,
derived from intralayer hopping between nearest-neighbor atoms, interlayer
vertical hoppings between nearest- and next-nearest-neighbor planes, and non-
vertical hopping between nearest-neighbor planes. The zero-field Hamiltonian
matrix in the subspace of a tight-binding basis {φA, φB} is expressed as
(
 α 1h + α 2 h 2 − 2
H AA = 
) (α 0 + α 3 h) f (kx , k y )
, (2.5)
(
 (α 0 + α 3 h ) f * k x , k y ) (
α 1h + α 2 h 2 − 2 ) 
where:
3
f (k x , k y ) = ∑exp(ik ⋅ r ) = exp(ibk ) + exp(ibk /2)cos(

j =1
j x x 3 bk y /2) represents
the phase summation arising from the three nearest neighbors

h = 2cos(kzIz)
The kz-dependent terms are involved in the matrix elements due to the
periodicity along the z-direction. The π-electronic energy dispersions are
obtained from diagonalizing the Hamiltonian matrix in Equation 2.5:
 h2 
( )
E±c , v k x , k y , k z = α 1h + 2α 2 
 2 − 1 
(
± (α 0 + α 3 h ) f k x , k y , ) (2.6)
and wave functions are

Ψc±,,vk =
1 
ϕ Al , k ±
(
f * kx , ky )

ϕ Al , k  . (2.7)
2
 (
f kx , ky )

The superscripts c and v, respectively, represent the conduction and valence
states.
As a result of the vector-potential-induced phase, the number of bases in
the primitive unit cell is increased by 2RB times compared to the zero-field
case. Using the Peierls substitution of Equation 2.4 and considering only the
neighboring atoms coupled by α’s, one can derive a band-like form for the
magnetic Hamiltonian matrix of AA-stacked graphite:
Bmk |H |Bm′k = Amk |H | Am′k = α 1h + α 2 h 2 − 2  δ m , m′ , ( ) (2.8)
(
Amk |H |Bm′k = (α 0 + α 3 h ) t1k ( m) δ m , m′ + qδ m −1, m′ . ) (2.9)
The eigenvector is expanded in the bases with the specific sequence

{ A1k , B2 RB k , B1k , A2 RB k , ........BRB k , ARB + 1k } and the three independent phase
terms are expressed as
{
t1k ( m) = exp i  − ( k x b/2) −
 ( )
3 k y b/2 + πΦ ( m − 1 + 1/6 ) +
 }
{
exp i  − ( k x b/2) +
 ( )
3 k y b/2 − πΦ ( m − 1 + 1/6 ) ,
 } (2.10)
q = exp (ik x b ) ,
where Φ is the magnetic flux through each hexagon. By diagonalizing the
Hamiltonian matrix, the kz-dependent energies and wave functions of the
valence and conduction LSs are thus obtained. Such a band-like matrix
spanned by a specific order of the bases is also applicable to other prototype
bulk graphites. In addition, when the low-energy approximation, in relation
to the Dirac points, is made for the Hamiltonian matrix in Equation 2.5, the
LS’s spectrum is further evaluated from magnetic quantization (discussion
in Section 3.3.2) [55]. However, the conservation of 3D carrier density needs
to be included in this evaluation.
2.1.2 Bernal Graphite

Bernal graphite is the primary component of natural graphite. The primi-
tive unit cell comprises A1, B1, A2 and B2 atoms on two adjacent layers,
where A1 and A2 (B1 and B2) are directly located above or below A2 and
A1 (the centers of hexagons) in adjacent layers, a configuration named
AB stacking (Figure 2.1b). The critical atomic interactions based on the
Slonczewski–Weiss–McClure (SWM) model cover γ0, , γ5, which are inter-

preted as hopping integrals between nearest-neighbor and next-nearest-
neighbor atoms, and additionally γ6, which refers to the difference of the
chemical environments between non-equivalent A and B atoms. The values
are as follows: γ0 = 3.12 eV, γ1 = 0.38 eV, γ2 = −0.021 eV, γ3 = 0.28 eV, γ4 = 0.12 eV,
γ5 = −0.003 eV and γ6 = −0.0366 eV [46].
The tight-binding Hamiltonian is described by a 4 × 4 matrix, which,
expanded in the basis {φA1, φB1, φB2, φA2}, takes the form
 EA (
γ 0 f kx , ky ) γ 1h ( ) 
γ 4 hf * k x , k y
 
H AB =
*
(
 γ 0 f kx , ky ) EB *
γ 4 hf (k x , k y ) γ3 hf ( k , k ) 
%
x y
( ) f ( k , k ) 
* (2.11)
 γ 1h γ 4 hf k x , k y EA γ0 x y
(
 γ 4 hf k x , k y ) γ3 hf ( k , k )
*
x y (
γ 0 f kx , ky ) EB 
where EA = γ6 + γ5h2/2 and EB = γ2h2 / 2. These indicate the sum of the on-site
energy and hopping energy of A and B atoms, respectively.
Energy bands and wave functions are easily calculated by diagonalizing
the Hamiltonian matrix.
At B = B0 zˆ , the magnetically enlarged unit cell includes 2 × 4RB bases,
which constructs the kz-dependent Hamiltonian matrix with non-zero terms
only between neighboring sublattices on same and different layers. An
explicit form of the matrix element is given by
(
Bm1 k |H | Am1 ′k = − γ 0 t1k ( m) δ m , m′ + qδ m + 1, m′ , ) (2.12)
(
Bm1 k |H | Am2 ′k = γ 4 h t1k ( m) δ m , m′ + qδ m + 1, m′ , ) (2.13)
Am2 k |H | Am1 ′k = γ 1hδ m , m′ , (2.14)
(
Bm2 k |H |Bm1 ′k = γ 3 h t2 k ( m) δ m , m′ + qδ m + 1, m′ , ) (2.15)
(
Am2 k |H |Bm2 ′k = − γ 0 t3 k ( m) δ m −1, m′ + qδ m , m′ , ) (2.16)
(
Am1 k |H |Bm2 ′k = − γ 4 h t3 k ( m) δ m −1, m′ + qδ m , m′ , ) (2.17)
Am1 k |H | Am1 ′k = Am2 k |H | Am2 k ′ = EAδ m , m′ , (2.18)

Bm1 k |H |Bm1 ′k = Bm2 k |H |Bm2 k ′ = EBδ m , m′ (2.19)
where:
t1k(m) and q are shown in Equation 2.10
t2k(m) and t3k(m) are expressed as
{
t2 k ( m) = exp i  −(k x b/2) −
 ( 3k b/2) + πΦ (m − 1 + 3/6)}
y
+ exp {i  − ( k b/2) + ( 3 k b/2) − πΦ ( m − 1 + 3/6 )} ;

 x y

(2.20)
t3 k (m) = exp {i  − (k b/2) − ( 3 k b/2) + πΦ (m − 1 + 5/6)}
x y
+ exp {i  − ( k b/2) + ( 3 k b/2) − πΦ ( m − 1 + 5/6 )} .

 x y

It should be noted that the calculations based on the effective-mass approx-

imation have trouble with the infinite order of the Hamiltonian matrix
induced by the significant interlayer hopping integral of γ3 [29,30]; this diver-
gence also exists for ABC-stacked systems [264]. Nevertheless, through a
qualitative perturbation analysis of γ3 and other interlayer interactions, the
minimal model, which regards γ0 and γ1 as the unperturbed terms, describes
effectively the low-energy dispersions in the vicinity of the vertical edges in
the first Brillouin zone. The generalized Peierls tight-binding model, which
retains all important atomic interactions and magnetic fields, however, can
provide comprehensive descriptions for graphites that offset the limitations
of accuracy at low energies.
2.1.3 Rhombohedral Graphite

For ABC-stacked graphite, called rhombohedral graphite, the unit cell is cho-
sen along the z-direction (Figure 2.1c). There are six atoms in a unit cell. The
interlayer atomic interactions, based on the SWM model, take into account
the nearest-neighbor intralayer interaction β0 = −2.73 eV and five interlayer
interactions β1 = 0.32 eV, β2 = −0.0093 eV, β3 = 0.29 eV, β4 = 0.15 eV and β5 = 0.0105
eV, in which the former two refer to vertical atoms and the latter three are
non-vertical [111]. The Hamiltonian matrix can be expressed as a combina-
tion of nine 2 × 2 submatrices for simplicity:
 H1 H2 H 2 
H ABC =  H 2 H1 H2  , (2.21)
 
 H 2 H 2 H1 
Where H1 and H2 take the forms

H1 = 
0 (
β0 f k x , k y  )
; (2.22)
*
(
 β0 f k x , k y ) 0 
( ) (
 β 4 exp (ik z I z ) + β 5 exp ( −i 2k z I z ) f * k x , k y )
H2 = 
(
 β exp (ik I ) + β exp ( −i 2k I ) f k , k
 3 z z 5 z z x) ( y )
β1 exp (ik z I z ) + β 2 exp (i 2k z I z ) 
. (2.23)
(β 4 ) (
exp (ik z I z ) + β 5 exp ( −i 2k z I z ) f * )
k x , k y 
It is also noted that the hexagonal unit cell used here is not the primi-
tive unit cell of rhombohedral graphite. The primitive unit cell should be a
rhombohedral form that consists of two atoms and is inclined to the z-axis
by an angle θ = tan −1 (b/2/I z ) (Figure 2.1c). That is to say, the bases of the
primitive unit cell are reduced from 6 to 2, as the rhombohedral unit cell is
selected instead of the hexagonal one [110]. The Hamiltonian has an analytic
solution near the zone edges H-K-H by using a continuum approximation
[111,132,265]. This reflects the fact that the energy dispersions in the hexago-
nal cell can be zone-folded to the primitive rhombohedral one, and that the
inversion symmetry is characterized similarly to that of simple hexagonal
graphite. As a result, the physical properties of rhombohedral graphite might
present certain features similar to those of monolayer graphene or simple
hexagonal graphite, and their difference is only the degeneracy of energy
states. A comparison between rhombohedral and hexagonal unit cells is
made in detail in Chapter 5.
At B = B0 zˆ , the magnetically enlarged rectangle cell is chosen as the
enlargement of the hexagonal unit cell along the z-axis for the convenience
of calculations. Such a rectangular cell includes 3 × 4RB atoms and the
Hamiltonian matrix elements are given by
(
Bm1 k |H | Am1 ′k = β0 t1k ( m) δ m , m′ + qδ m , m′ −1 , ) (2.24)
(
Bm2 k |H | Am2 ′k = β0 t3 k ( m) δ m , m′ −1 + qδ m , m′ , ) (2.25)
(
Bm3 k |H | Am3 ′k = β0 t3 k ( m) δ m , m′ + qδ m , m′+ 1 , ) (2.26)
( )
Am1 k |H |Bm2 ′k = Am2 k |H |Bm3 ′k = Bm1 k |H | Am3 ′k = β1e i 3 kz I z + β 2e −6 ikz I z δ m , m′ ,
(2.27)
( )(
Am3 k |H |Bm2 ′k = β 3 e ikz I z + β 5e −6 ikz I z t1k ( m) δ m , m′ −1 + qδ m , m′ ,) (2.28)
( )( )
Am2 k |H |Bm1 ′k = β 3 e i 3 kz I z + β 5e −6 ikz I z t2 k ( m) δ m , m′ + qδ m , m′+ 1 , (2.29)
( )(
Am1 k |H |Bm3 ′k = β 3 e ikz I z + β 5e −6 ikz I z t3 k ( m) δ m , m′ −1 + qδ m , m′ ,) (2.30)
( )( )
Bm1 k |H |Bm2 ′k = β 4 e i 3 kz I z + β 5e −6 ikz I z t2 k ( m) δ m , m′ + qδ m , m′+ 1 , (2.31)
( )(
Am1 k |H | Am2 ′k = Bm2 k |H |Bm3 ′k = β 4 e − i 3 kz I z + β 5e 6 ikz I z t3 k ( m) δ m , m′ −1 + qδ m , m′ ,)
(2.32)
( )(
Am2 k |H | Am3 ′k = β 4 e − i 3 kz I z + β 5e 6 ikz I z t2 k ( m) δ m , m′ + qδ m , m′+ 1 ,) (2.33)
( )( )
Bm3 k |H |Bm1 ′k = β 4 e − i 3 kz I z + β 5e 6 ikz I z t2 k ( m) δ m , m′ + qδ m , m′+ 1 ; (2.34)
( )(
Am3 k |H | Am1 ′k = β 4 e − i 3 kz I z + β 5e 6 ikz I z t1k ( m) δ m , m′ + qδ m , m′+ 1 . ) (2.35)
The independent phase terms t1k(m), t2k(m), t3k(m) and q are shown in
Equations 2.10 and 2.20. The generalized tight-binding model, accompa-
nied by an exact diagonalization method, can further be applied to study
other physical properties, such as the optical absorption spectra [18,56–
58,88,137,138] and plasma excitations [59,61,382]. Different kinds of external
fields, for example, a modulated magnetic field [174], a periodic electric
potential [175] and even a composite field [176], could also be included in
the calculations simultaneously. Furthermore, this model can be applied
to other layered materials with a precisely chosen layer sequence, such
as graphene, MOS2 and silicene, germanene, tinene and phosphorene
[177–181]. The electronic structures and characteristics of wave functions
are well depicted and the results are accurate and reliable within a wide
energy range.
2.1.4 Gradient Approximation for Optical Properties

When graphite is subjected to an electromagnetic field, the optical spectral
function A(ω) is used to describe its optical response. At zero temperature,
A(ω) is expressed as follows according to the Kubo formula:
2
⋅P
∑∫ ( ) ( )
dk E
A (ω ) ∝ Ψck nc Ψvk nv
1stBZ ( 2π )
2
me
nv , nc
(2.36)
× Im  c c
( )
 ( )
 f Ekc nc  − f Ekv nv  
   ,

( ) ( )
 Ek n − Ek n − ω − lγ 
v v
where the definite integral spans over the first Brillouin zone (1st BZ), Ê is
the direction of electric polarization, P is the momentum operator, f [Ek(n)] is
the Fermi-Dirac distribution, me is the electron mass and γ is the phenomeno-
logical broadening parameter. Ê, which lies on the (x, y) plane, is chosen for a
model study. nc,v is the energy band index measured from the Fermi level at
zero field, or it represents the quantum number of each LS. The integration
for all wave vectors is made within a hexahedron (a rectangular parallelepi-
ped) in a zero (non-zero) magnetic field. The initial and final state satisfy the
condition of Δk = 0, which is responsible for the zero momentum of photons.
This implies that only the vertical transitions are available in the valence
and conduction bands. Using the gradient approximation [18,57], the velocity
matrix element is evaluated from

( )
Mkc,v nc , nv = Ψck nc ( ) Em⋅ P Ψ (n )e
v
k
v
( )
~ Ψck nc ∂ ky H Ψvk nv ( ) || y.
for E
(2.37)
According to Equations 2.1, 2.5, 2.11 and 2.21, the velocity matrix elements
of simple hexagonal, Bernal and rhombohedral graphite are given by
c,v
MAA (
nc , nv , k )
 0 (α 0 + α 3 h ) ∂ k f   C Av , k  (2.38)
(
= C Ac , k )
CBc , k 
 (α 0 + α 3 h ) ∂ k y f
*
0
y
  Cv  ,
  B, k 
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To arrive there in time we should have to take the train next
morning. I went accordingly to the princess, who was the only person
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assistance.
I called on her at nine o’clock in the morning. I was taken to the
second storey of the palace, to a room that was even prettier, if
possible, than the one in which I had been received the first time.
The princess received me. She was in her night-robe, and had
put on a dressing-gown of white silk over which her beautiful
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I asked her what she liked best among all the things there and
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“This is my room,” she said, while we were talking, “in which
whatever happens no one is permitted to bother me. I take refuge
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I then told her my troubles. She rang a bell, and gave an order to
let M. X—— know immediately that Miss Fuller would come to see
him with a card from her, and that M. X—— would kindly do
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“I should have liked greatly to know you without being aware that
you were a princess.”
“But,” she said, “it is the woman whom you now know and not the
princess.”
And that was true. I felt that I was in the presence of some one
who was really great, even if her birth had not made her so. I am
certain that she would have accomplished great things if she had not
found her career already mapped out for her from the day of her birth
in her father’s palace.
Everyone knows that a princess’ life precludes liberty, and
contains no possibility of breaking with the conventions for the sake
of doing something extraordinary or notable. These chains are so
strong that if one contrives to break them, it generally happens under
the impulse of despair, as a result of irritation and not for the sake of
a purely inspired work.
When I arose to take leave of the princess she kissed me and
said:
“If ever I come to Paris I shall call on you at your studio.”
She caused an attendant to accompany me to the master of
ceremonies, with whom I was to go to the bank. There the master of
ceremonies communicated Princess Marie’s order to the effect that I
was to be accommodated in any way I might desire.
The money I needed was advanced in return for a cheque, and I
left Bucharest.
The journey was full of troubles. Vexatious delays occurred.
Finally I arrived at Rome, where my appearance had to be
postponed until my baggage, lost in transit, had been found. Three
thousand people, who had come to my first performance, went away
without seeing me. That certainly was very hard luck. If I had been
able to foresee all that, I should never have ventured to intrude upon
the Princess.
In that case I should not have discovered what an admirable
woman she is.
XV
SEVERAL SOVEREIGNS
I N the course of my travels about the world, east, west, north and
south, over oceans and across continents, I have had the
experience of seeing or of encountering many persons of
distinction, including not a few sovereigns and members of royal
households.
It has seemed to me that it might be interesting to bring together
at this point some of the most typical of the incidents that occur to
me. Just as they come, drawn haphazard from memory, without
order or sequence, and with no thought of literary composition, I am
going to put them simply on paper, one by one.
How I Failed to see Queen Victoria.

One day at Nice some one came and asked me to dance before
Queen Victoria. She had just arrived on the Riviera to pass the
winter months, as she was accustomed to do every year.
It may well be believed that I was flattered by such a request. I
assented, naturally, and set myself to work making all my
preparations for this important event.
There was a knock at the door. A maid brought a telegram. It was
signed by my manager, and was couched in the following words:
“Take train this evening, to sail day after to-morrow; destination, New
York.”
I replied with a message pleading for a delay, for the purpose of
dancing before Queen Victoria.
I received simply the following laconic telegram:
“Impossible. Leave at once. Time is money.”
That’s why I did not dance before Queen Victoria.
I stop the Queen of the Belgians in the Street.

I was engaged for some performances at Spa. The evening of my
first appearance the Queen and Princess Clementine were in the
royal box. That was a gala evening, one on which the hall was
resplendent with magnificent gowns and jewels.
Everything went off perfectly.
Next morning I went for a walk with my mother. We were crossing
the causeway when a carriage, drawn by two spirited horses driven
by a middle-aged woman, bore down upon us.
Frightened on account of my mother, I threw up my arms in front
of the carriage, which stopped.
The lady allowed us to pass and, while thanking her, I remarked
to myself that a woman ought not to drive such lively horses.
I had forgotten the incident when, shortly after my return to the
hotel, I saw the same carriage go by.
Two gentlemen were talking on the landing near us.
“See. There is the Queen,” said one of them.
It was the Queen whom I had stopped!
Princely Simplicity.
At the Hague I was asked to give a performance before the
Grand Duke and Duchess of Mecklenburg, Princess Victoria of
Schaumburg-Lippe and their retinue.
The hall was well filled. I had the Philharmonic Society’s
orchestra.
This was a gala evening, and in every way a very successful one
for me.
Next day on coming down from my room I encountered on the
stairway of the hotel a lady with a very sweet expression, who asked
me:
“You are Miss Loie Fuller? Your dances interest me greatly. My
husband has gone out on the beach. Wouldn’t you like to come and
talk to him about your lighting effects. I am sure that would prove
very interesting to him.”
I gladly acquiesced and followed her.
I was delighted to talk to this woman and her husband, who
proved to be a most delightful man. I explained to them all my
schemes of lighting and my dances. I then took my leave and joined
my mother, who was waiting for me.
When I returned to the hotel the proprietor came to me and said:
“You met with great success yesterday, Miss Fuller, and with
even greater this morning.”
“This morning?”
“Yes. Do you know who the gentleman is with whom you have
just been talking?”
“No. Who is he?”
“The Grand Duke of Mecklenburg.”
This same day I boarded a street car.
On the car several people appeared to know me. One lady came
and sat beside me and began to talk.
When we arrived at our destination I asked her if she would not
tell me her name.
“Victoria de Schaumburg-Lippe.”
One evening when I was dancing at the Hague the princess was
in the hall with Major Winslow and others of her retinue. She sent for
me, and asked me to show her one of my robes.
I brought her the robe which I put on for the butterfly dance.
She took the stuff in her hand and said:
“The robe is really wonderful, but it is after all only what you do
that counts.”
I remember that she asked me to sign a photograph for her. And
when I returned to the hotel the manager of the Kurhaus handed to
me an exceedingly pretty watch, on the cover of which were
engraved these words:
“In memory of the performance given for Princess Victoria.”
The Curiosity of the Archduchesses of Austria.

I was once at the Swedish gymnasium at Carlsbad, where
machines with electrical vibrations shock you from head to foot. I
was just about to dress myself when one of the women of the place
came to me, and said:
“Won’t you please return to the hall, and pretend to take the
electric treatment again in order that the archduchesses, who are
there, with a whole crowd of court ladies, may see you?”
I replied: “Tell the archduchesses that they can see me this
evening at the theatre.”
The poor woman then declared to me that she had been
forbidden to mention their Royal Highnesses, and that they had
bidden her get me back into the hall on some pretext or other.
She was so grieved at not having succeeded that I returned to
the machines, and had my back massaged, in order that the noble
company might look at me at their ease, as they would survey an
interesting animal.
They looked at me, all of them, smiling, and while they viewed
me I never turned my eyes away from them.
The odd thing was that they did not know that I knew them. I was,
therefore, as much amused by them, and without their perceiving it,
as they were amused by me.
How I was not decorated with the Order of the Lion
and the Sun of Persia.
During one of the visits that the Shah of Persia pays to Paris, the
Marquis and Marquise d’Oyley, who were great friends of the
Sovereign and who were very fond of my dancing, brought the Shah
to one of my performances at Marigny.
After my appearance on the stage the Marquis and Marquise,
accompanied by some dignitaries of the sovereign’s retinue, came to
my dressing-room and brought me a Persian flag, which they
begged me to use in one of my dances.
What could I do with that heavy flag? In vain I racked my brain. I
could not discover any way. I could not refuse, and I was unable on
the other hand to convince them that it was impossible to try
anything so impromptu without running the risk of a failure.
More and more perplexed I made my entrance for the last dance.
I had the great flag in my arms. I tried to wave it gracefully, but I did
not succeed. I tried to strike a noble attitude, still holding the flag.
Again I failed. It was a woollen banner and would not float. Finally I
stood stock still, holding the staff upright, in as imposing an attitude
as possible. Then I bowed until the curtain fell.
My friends were surprised to observe that my last dance had
displeased his Majesty. The Shah finally told them that he did not
see why the Persian flag had been desecrated. No one dared to tell
him that the idea had not come from me, but from persons of his
retinue, or to inform him how I had received the flag.
My friends, the d’Oyleys, consoled me by saying that my pose
had been very noble and that even the flag, falling around me in
heavy folds, had produced a very striking effect.
The Shah decorates everybody who has attracted his attention;
that is a habit he has acquired. For my part, thanks to the brilliant
idea of the dignitaries from the court of Teheran, I have never seen
either the tail of the Lion or a ray of the Sun peculiar to Persian
decoration.
I have been told on other authority that on this evening the
Shah’s first thought was of a bomb which, so it had been announced,
was to be thrown at him in the hall. He was thinking of this rather
than of my person, my dances or even of the Persian flag I
“profaned.”
My Adventure with a Negro King.

At the Colonial exposition in Marseilles in 1907 I was with some
friends in the pavilion of one of the exhibitors when a magnificent
negro, six feet high, who looked like some prince from the Thousand
and One Nights, came upon the terrace where we sat. He was
accompanied by a large retinue. The other negroes were dressed
the same as he, but none of them had his magnificent presence.
Some French officials accompanied the visitors, who, naturally,
created a tremendous effect with their costumes, which were simple
but exquisitely finished. When they came near I exclaimed:
“He might be called a king out of a fairy tale!”
They passed before us and took their places in the reception hall.
The proprietor presently came to our group, and asked us if we
would not like to assist him in receiving the King of Djoloff in
Senegal.
“He is visiting the Exposition as a private citizen,” he added. “If
you would like to make his acquaintance come and I will present
you.”
I was charmed.
When I was in the presence of the king, I said quietly to my
friends, in a distinct voice and in French:
“What a handsome savage; I wonder if they are all built on this
model in Africa.”
I was presented to the king. He extended his hand, and, to my
consternation, I heard him say in very good French:
“I am delighted to make your acquaintance, Miss Fuller. I have
applauded you frequently. My education was gained in Paris.”
I could not repress an exclamation.
“Good heavens! Then you heard what I said, and you never
raised an eyelash!”
“No, since you did not suppose that I understood you.”
I looked at him for a minute or two to find out whether he had
been irritated or not. He smiled diplomatically and I felt that we
should be friends.
I was dancing at Marseilles at that time. He came to the theatre
to see me after the performance.
“What can we do that will give you pleasure in exchange for the
great satisfaction that your dances have just brought us?” he asked
me.
I thought the matter over a minute.
“I should like it very much if I might be present at one of your
religious ceremonies.”
The black chief promised to come to my hotel, and to give me an
idea of the ritualistic practices of his country.
The next day, accordingly, I made preparations for a tea-party in
the hotel garden. Rugs were spread on the grass and everything
was in readiness to receive the monarch.
“When will the ceremony begin?” I asked the king as soon as he
had arrived.
“We shall say our prayer at six o’clock, just at sunset.”
As night came on I observed that the king and his followers
began to survey the sky in every direction, and I wondered why.
Noting my wonderment, the king told me that they were
endeavouring to get their bearings in order to be certain of the point
toward which the sun was tending at the end of his journey.
“We are required,” he said, “always to pray with our faces toward
the setting sun.”
He gave the order to begin the ceremony then and there. I wish I
could describe it as perfectly as I saw it.
The unity of the motions of all these men was simply wonderful.
All together they said the same brief prayer, and with mechanical
precision made the same movement, which, from the point of view of
devotion, seemed to have similar importance to the words of their
ritual. The large white cloaks, spread over long blue blouses, waved
round their bodies. The men prostrated themselves, touched the
ground with their foreheads and then raised themselves together.
The rhythm and precision were most impressive. It was really very,
very beautiful.
After the prayers the king told me that his father had been
dethroned and then exiled from Senegal by the French Government.
As for himself, in his turn he had been nominated chief of his tribe,
for in reality there was no longer a king. He was a French subject,
and in his country, which was tributory to France, he was no more
than chief of his clan.
But the majesty remained, nevertheless, magnificently expressed
in his features.
While we were conversing I asked permission to put some
indiscreet questions. After he had consented, all the while smiling his
peculiarly winning smile, I asked him if he was married?
He replied in the affirmative. He had four wives. As I appeared to
be surprised to note that he travelled without them, especially in a
country where there are so many pretty women, he, in his turn,
looked at me for some time, and replied:
“From the point of view of my wives a white woman has neither
charm nor beauty.”
This surprised me greatly, and I asked him whether that was
because they had never seen any white women.
“Oh,” he replied, “in any case they would not be jealous of a white
woman. It seems to them absolutely impossible that a pale-faced
woman can play any part in my life.”
“And you? Are you so sure of that? If a white woman with long
blonde hair should suddenly appear in your country, among your
black women, would she not be taken for an angel?”
“Oh, no. She would be taken for a devil. Angels are black in our
Paradise.”
This, I must confess, opened new vistas in the domain of religion.
It had never before appeared so clear to me that men make their
gods in their own image, rather than that the gods make men after
theirs.
How the Empress of China Degraded a Mandarin on

my Account.
I was dancing in New York when several of Li Hung Chang’s
followers came to the theatre. Some friends presented me to the
American military attaché, Mr. Church, who accompanied the
Viceroy.
Thanks to Mr. Church I was able to satisfy my curiosity and
become acquainted with these high Chinese dignitaries. When they
left for their own country my manager went with them, in the hope
that, through their good offices, I might dance at the Chinese court in
the presence of the dowager Empress and her son.
As soon as my representative was in China, he cabled me that
everything had been arranged and that I was to take the first
steamer leaving Vancouver.
After crossing the continent I was on the point of embarking with

my mother, when the state of her health caused me the keenest
anxiety. Her prostration was so complete that I was obliged to send a
message to China, indicating the impossibility of keeping my
engagement.
My manager rejoined us utterly dejected.
At Pekin a magnificent reception had been prepared for me. I
was to dance before the Emperor and Empress and then in Japan I
was to appear before the Mikado. The theatre of the best Japanese
actor, Danjero, was to be put at my disposal. And all that to no
purpose whatever. My manager brought back from this oriental
country the most marvellous of embroideries, which Li Hung Chang
had sent over for me.
I experienced genuine regret at the failure of this trip, then I forgot
all about it.
One evening in London one of my friends at dinner found herself
seated next to a very high Chinese official. Apropos of the rich
colouring of the mandarin’s garments, they came to speak about me
and my coloured dances, and my friend said to her companion:
“You are acquainted with Loie Fuller, I presume.”
“Well, yes, madam,” he replied. “I am only too well acquainted
with her, if I may say so.”
“How is that?”
“I went to the United States with Li Hung Chang. Loie Fuller’s
manager accompanied us on our return to China, and, through the
influence of the Viceroy, we gained permission for Loie Fuller to
appear before the Empress. Just as she was about to leave for
Pekin she broke her agreement. It fell upon me to inform her Majesty
that Loie Fuller was unable to obey the Imperial mandate. The
Empress had me degraded! That was eight years ago. I lost my
yellow jacket, which has only recently been restored to me.”
My friend pleaded my case, alleging the condition of my mother’s
health, and the seriousness of her malady at the time of my failure to
report in the celestial empire.
I suppose that it would be too much to expect of His Excellency
to ask him to forgive my mistake. If I had known that my failure to
appear would be attended with such consequences, I should,
instead of cabling to my manager, have forwarded a long dispatch to
the Empress herself, telling her the reasons for my failure to keep an
engagement. A woman with a heart, even if she be an Empress,
could not blame a daughter for doing her duty towards her mother.
How Queen Alexandra did not fail to see me.

One morning the papers said that the King and Queen of
England were going to spend several days in Paris.
I was then dancing at the Hippodrome and, remembering what
Princess Marie of Roumania had told me, I decided not to let this
occasion slip, and I wrote to the Queen herself, asking if she would
be kind enough to set aside an hour in which I might give a
performance, at her own convenience and whenever she chose.
I should never, indeed, have supposed it possible to ask her to
come to the Hippodrome. One of her maids of honour answered the
note, saying that Her Majesty’s stay was of limited duration, and that
she had already accepted too many invitations to undertake any new
engagements.
After that I thought no more of the Queen.
Arriving at a matinee one Thursday, I noticed in front of the
Hippodrome quite an impressive line of carriages, all displaying the
royal insignia.
“The Queen has sent some one to my matinee,” I thought. “She
wants to know whether my dances are really worth seeing. If I make
a pleasant impression the Queen will perhaps some day ask me to
dance before her.”
I went into my dressing-room. I had nearly finished my
preparations when the manager rushed in post haste calling out:
“It’s four o’clock and the Queen has been waiting since half-past
two.”
“What! The Queen is here! Why didn’t you inform me sooner?”
He was too unnerved to make a lengthy explanation. I hurried
down and two minutes later I was on the stage.
In the middle of my dance the Queen arose and left the theatre
with all her attendants. I saw her rise and go!
I thought the floor would open and engulf me. What had I done to
offend her? Was she indignant that I had made her wait? Was this
her way of punishing me for my discourtesy, or did my dances
displease her? What was I to think?
I went home in utter despair.
I had just realised one of my dearest wishes, that of dancing
before the Queen. Never had I experienced such dejection. I should
have preferred a thousand times that she had not come.
I learned afterward at the theatre that a telephone message had
come shortly after noon to the effect that the Queen wished to see
Loie Fuller, but that she would have to leave at four o’clock.
The manager, who had supposed that the Queen was coming to
see the Hippodrome, had not attached any importance to the
intimation regarding me, and did not even take the trouble to find out
whether I was there or not.
Next morning all the papers recorded that the Queen of England
had come to the Hippodrome, despite her many appointments and
engagements made some time earlier, and so forth and so forth.
There was not a word about me.
However, as I had written to the Queen to ask her to come it
seemed to me that I ought to excuse myself for my apparent
discourtesy. I wrote to her accordingly, telling her how distressed I
was at my failure to appear earlier—a failure that would not have
occurred if some one had come to apprise me. I regretted that the
message had not been forwarded to me instead of to the manager.
That same evening one of my friends came to tell me that she
had written the day before to one of the Queen’s maids of honour,
whom she knew personally, asking her to come and see me dance
at the Hippodrome.
Photo Lafitte
THE DANCE OF THE BUTTERFLY
“That will make your new dances celebrated all over the world,”
said my friend. “The Queen will come, I am certain of it, if it is at all
possible.”
Overcome with surprise, I looked at my friend, and exclaimed:
“Well, then, that is why she came this afternoon!”
“Has she already come to see you? I should not have expected
such promptness.”
“She came to the matinee.”
And I told my friend the whole story in detail.
She still could not understand why the Queen had left so hastily,
and enquired into the reason.
Presently everything was explained.
The Queen had agreed to visit a painter’s studio at half-past
three and then, at four o’clock, to call upon M. and Mme. Loubet.
Nevertheless she remained at the Hippodrome until ten minutes past
four. The King went alone to the studio and the Queen arrived late at
the President’s house.
After that I fully appreciated her kindness, her patience. I still feel
endless gratitude to her for having waited so long, for not having left
the theatre without seeing, if it was only for a moment, Loie Fuller
and her dances.
As for the manager, he is still convinced that the Queen did not
come to see Loie Fuller, but the Hippodrome, and only the
Hippodrome.
XVI
OTHER MONARCHS
I SHALL always remember with great pleasure my six hundredth

appearance in Paris.
I was then dancing at the Athénée. The whole house had been
bought up by students. When I came on the stage each spectator
threw a bunch of violets at me. It took five minutes to gather up the
flowers.
When I had finished dancing, a fresh avalanche of flowers poured
upon the stage. During the performance I received from my
admirers, along with an album of sketches signed with names,
several of which are now famous, an exquisite statuette representing
me in a characteristic attitude.
When I was ready to leave the theatre, the students took my
horses out of the shafts and drew my carriage themselves. At the
Madeleine the crowd was so dense that the police warned us to
stop. But as soon as they had learned that it was “La Loie” in whose
honour the triumphal procession was decreed, we had permission to
go our way without interruption. The young men drew my carriage all
the way to Passy, where I lived. They conscientiously awakened all
the inhabitants with their outcries.
Finally we reached the house. I did not know what I was going to
do with these boys, but they themselves solved the problem without
delay.
After they had rung the bell and as soon as my gate had swung
on its hinges they emitted a shout all together, and started to run
away as if possessed. I could hear them for a long time afterwards,
shouting: “Vive l’art! Vive La Loie!”
I have often wondered whether the police were as lenient on their
return.
In Marseilles, at the time of the Colonial Exposition, one of the
commissioners of fine arts asked me if I would not like to perform
out-of-doors.
That was one of my dearest wishes, and I consented readily.
Preparations were made at once for my performance, which was
to be given in the same place where we had admired the King of
Cambodia’s dancers. The stage was built opposite to the Grand
Palais.
The director of the Exposition had placed behind the platform
some great plants, in order that I might be relieved against a
background of green foliage, which would be particularly favourable
to the brilliancy of the figures in the foreground. Below the stage
were two little ponds, with sparkling fountains.
The evening of my first appearance arrived. I was feverishly
impatient.
Nothing had been done to advertise it to the public of Marseilles,
for we regarded this first evening as a kind of rehearsal, which we
should repeat a week later, if it met with success. It was only this
next performance that we expected to announce formally.
It was a starlight night. There were at least thirty thousand visitors
at the Exposition.
The lights were put out and the crowd rushed towards the
platform. In spite of its impromptu character the performance was a
remarkable success, and the committee decided from this time on to
continue to give outdoor performances.
During the second evening, just as the lights were about to be
extinguished, a man came and said to me as I was on my way to the
stage:
“Just look, before they put the lights out, at the human wave
curling at your feet.”
I had never seen anything like it.
After the electric lights had been shut off I began to dance. The
rays of light enveloped me. There was a movement in the crowd,
which reverberated in echoes like the mutterings of a storm.
Exclamations followed, “Ohs” and “Ahs,” which fused into a sort
of roar, comparable to the wailing of some giant animal.
You can hardly imagine anything like it. It seemed to me that on
my account alone this spectacle was presented by all this moving
crowd before me.
A calm ensued. The orchestra, not a very large one, seemed to
me utterly ineffective in such a space. The audience, which was
seated on the other side of the fountains, certainly could not hear it.
The first dance came to its close. The extinguishing of my lighting
apparatus left us, the public and me, in utter darkness. The uproar of
the applause became something fantastic in the dead of night. It was
like the beating of a single pair of hands, but so powerful that no
noise in the world could be compared with it.
I danced four times, and the different sensations expressed by
the audience were most remarkable. They gave me the most vivid
impression I have ever experienced. It was something immense,
gigantic, prodigious.
That day I had a feeling that the crowd was really the most
powerful of monarchs.
There are other monarchs as well as kings and crowds. Certain
emotions are kings, too.
At Nice, at the Riviera Palace Hotel, I noticed one day at a table
near mine a young man of distinguished appearance whose glance
met my own several times successively, almost, one would fancy, in
spite of himself. During the following days we surveyed each other
again and again at meal times, but without progressing further
towards acquaintance.
I had a number of friends with me. He was alone. Gradually my
heart went out to him, although we had never exchanged a word. I
did not know who he was, and I had no notion of seeking his
acquaintance. Yet his brown eyes and his type of personality, calm
and simple, exerted a sort of fascination over me. A week later I
discovered, to my great confusion, that I was perpetually haunted by
his eyes and that I could not forget his smile.
One evening there was a ball at the hotel. I was invited, of
course.
As I have already said, I had a great many friends there. All at
once, in a corner, I noticed my neighbour of the dining-hall. He spoke
to no one. He was not dancing. I began to feel sorry to see him so
entirely alone. My sympathy went out more than ever towards him.
Some days later I was engaged for a performance that was to
take place at the hotel in honour of a Russian grand duke, two kings
and an empress.
I remember that Patti was in the front row. When I appeared
before this choice assembly, a single figure persisted in detaching
itself from the rest of the crowd. It was the figure of my unknown
young man. Who could he be to be noted thus, in the role of an
invited guest, among these princes and princesses? He rested his
elbow on the back of his chair. His hand was under his chin. His legs
were crossed with easy negligence. He looked at me continuously.
Everybody applauded over and over again. He alone did not lift a
finger.
Who was this man? Why did his countenance haunt me? Why
did he watch me so insistently? Why did he not join in the applause?
The next day, on the verandah, I was comfortably seated in a
rocking-chair, all the while wondering who my handsome dark man
could be. Coming back to earth I saw him there by my side,
ensconced in one of those odd willow seats that enclose you as in a
sentry box.
His eyes again met mine. We did not speak, but both of us
experienced a deep desire to exchange greetings. Just at that
moment the hotel manager came up and began to talk to us. Then,
observing that we were not acquainted, he introduced us. I learned
then that he was son of an industrial leader of international standing

Textbook Electronic and Optical Properties of Graphite Related Systems 1St Edition Chiun Yan Lin Ebook All Chapter PDF

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Electronic and Optical Properties of

Graphite-Related Systems 1st Edition

Geometric and Electronic Properties of Graphene-Related

Optical properties of materials and their applications

Nanostructured Semiconductor Oxides for the Next

Silicon Germanium SiGe Nanostructures Production

Electronic Magnetic and Optical Materials 2nd Edition

Fundamentals of Surface Thermodynamics: Phase Behavior

Systems for Big Graph Analytics 1st Edition Da Yan

Control of Power Electronic Converters and Systems 1st

© 2018 by Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13: 978-1-138-57106-8 (Hardback)

Visit the Taylor & Francis Web site at

and the CRC Press Web site at

2 Theoretical Models and Experimental Techniques.................................9

3 Simple Hexagonal Graphite........................................................................ 29

6 Quantum Confinement in Carbon Nanotubes and

7 Concluding Remarks.................................................................................. 113

This book is intended as an introduction to the electronic and optical

Chiun-Yan Lin, Rong-Bin Chen,

Rong-Bin Chen is a professor at the Center of General

Yen-Hung Ho received his PhD in physics in 2009 from

Chiun-Yan Lin obtained his PhD in 2014 in physics from

Ming-Fa Lin is a distinguished professor in the

Carbon atoms can form various condensed-matter systems with unique

properties, for example, the special structures in density of states (DOS)

semimetallic, 3D electronic structure can be further comprehended through

ABC-stacked graphite has a rhombohedral unit cell, while AA- and

can be produced by cutting few-layer graphenes [155,156], unzipping mul-

of the magnetic Hamiltonian and the efficient combination of two meth-

In the presence of a uniform magnetic field, B = B0 zˆ, electrons are forced

2.1 Magnetic Tight-Binding Model for Layered Graphites

In general, the essential physical properties are mainly determined by 2pz

The effective momentum in the presence of B is P − eA/c, so that the 3D

where o and e, respectively, represent the odd-indexed and even-indexed

2.1.1 Simple Hexagonal Graphite

f (k x , k y ) = ∑exp(ik ⋅ r ) = exp(ibk ) + exp(ibk /2)cos(

the phase summation arising from the three nearest neighbors

and wave functions are

Bmk |H |Bm′k = Amk |H | Am′k = α 1h + α 2 h 2 − 2  δ m , m′ , ( ) (2.8)

The eigenvector is expanded in the bases with the specific sequence

2.1.2 Bernal Graphite

Slonczewski–Weiss–McClure (SWM) model cover γ0, , γ5, which are inter-

Am2 k |H | Am1 ′k = γ 1hδ m , m′ , (2.14)

Am1 k |H | Am1 ′k = Am2 k |H | Am2 k ′ = EAδ m , m′ , (2.18)

Bm1 k |H |Bm1 ′k = Bm2 k |H |Bm2 k ′ = EBδ m , m′ (2.19)

+ exp {i  − ( k b/2) + ( 3 k b/2) − πΦ ( m − 1 + 3/6 )} ;

+ exp {i  − ( k b/2) + ( 3 k b/2) − πΦ ( m − 1 + 5/6 )} .

It should be noted that the calculations based on the effective-mass approx-

2.1.3 Rhombohedral Graphite

2.1.4 Gradient Approximation for Optical Properties

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How Queen Alexandra did not fail to see me.

I SHALL always remember with great pleasure my six hundredth

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