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Coherent Light-Matter Interactions in
Monolayer Transition-Metal
Dichalcogenides 1st Edition Edbert
Jarvis Sie (Auth.)
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Springer Theses
Recognizing Outstanding Ph.D. Research
Edbert Jarvis Sie
Coherent Light-
Matter Interactions
in Monolayer
Transition-Metal
Dichalcogenides
Springer Theses
Recognizing Outstanding Ph.D. Research

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Edbert Jarvis Sie
Coherent Light-Matter
Interactions in Monolayer
Transition-Metal
Dichalcogenides
Doctoral Thesis accepted by Massachusetts Institute of
Technology, Cambridge, MA, USA
Edbert Jarvis Sie
Stanford University
Stanford, CA, USA
ISSN 2190-5053 ISSN 2190-5061 (electronic)

Springer Theses
ISBN 978-3-319-69553-2 ISBN 978-3-319-69554-9 (eBook)
https://doi.org/10.1007/978-3-319-69554-9
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Supervisor’s Foreword
Monolayer transition metal dichalcogenides (TMDs) such as MoS2 and WS2 are
prime examples of atomically thin semiconducting crystals that exhibit remarkable
electronic properties. These materials have generated an enormous amount of
interest in the quantum materials community because, like graphene, they possess
an additional valley degree of freedom (DOF) that has the potential to be used as an
information carrier in next-generation electronics. Unlike graphene, the presence of
broken inversion symmetry in these materials induces bandgaps in each valley that
can be selectively populated with carriers through optical excitation, even though
the two valleys remain to be energetically degenerate locked by time-reversal
symmetry.
Dr. Edbert Jarvis Sie’s thesis made several key contributions to our understand-
ing of light-matter interactions in these materials. By applying coherent ultrafast
optical spectroscopy, Dr. Sie was not only able to study the dynamics of excitations
in these systems but also to optically control their properties.
In particular, he has developed an optical technique to control the valley DOF.
To do this, the degeneracy between the two valleys must first be lifted by breaking
time-reversal symmetry. While applying a magnetic field should in principle
accomplish this task, experiments so far show merely 1–2 meV of valley energy
splitting with fields accessible in common laboratories. Dr. Sie used intense circu-
larly polarized light pulses that are tuned slightly below the bandgap to mimic the
effect of a magnetic field. The light pulse dresses the electronic states such that the
state repulsion between these dressed states leads to a valley-dependent energy shift
(now known as the valley-selective optical Stark effect). He measured the energy
splitting between the two valleys induced by the circularly polarized pump pulse
with a spectrally broadband probe pulse by recording the energy shift of the exciton
absorption peak.
By using this technique on monolayer WS2, he demonstrated that the exciton
energy level in each valley can be selectively tuned because the optical Stark effect
in this material also obeys the valley selection rules with circularly polarized light.
He was able to achieve an energy splitting of 18 meV, which is extremely large,
v
vi Supervisor’s Foreword
comparable to what would be obtained using a magnetic field of ~100 Tesla.

This finding represents a clear demonstration of breaking the valley degeneracy
in a monolayer TMD, and it offers a novel way of controlling the valley DOF
using off-resonance circularly polarized light for next-generation valleytronic
applications.
After discovering the valley-selective optical Stark effect in TMDs by exciting
with slightly off-resonance light, Dr. Sie decided to study what happens in the case
of large detuning. When light with frequency ω is detuned away from a resonance
ω0, repulsion between the photon-dressed (Floquet) states can lead to a shift of
energy resonance. The dominant effect is the optical Stark shift (/ 1/(ω0 ω)),
but there is an additional contribution from the so-called Bloch-Siegert shift
(/ 1/(ω0 + ω)). Although it is common in atoms and molecules, the observation
of the Bloch-Siegert shift in solids has so far been limited only to artificial atoms
since the shifts were small (<1 μeV) and inseparable from the optical Stark shift.
Dr. Sie observed an exceptionally large Bloch-Siegert shift (~10 meV) in mono-
layer WS2 under infrared optical driving. Moreover, he was able to disentangle the
Bloch-Siegert shift entirely from the optical Stark shift, because the two effects are
found to obey opposite selection rules at different valleys. By controlling the light
helicity, he was able to confine the Bloch-Siegert shift to occur only at one valley
and the optical Stark shift at the other valley. This discovery is quite important since
such a valley-exclusive Bloch-Siegert shift allows for enhanced control over the
valleytronic properties in two-dimensional materials.
Dr. Sie also presents a number of other key results especially on many-body
interactions between excitons in TMDs. For example, interactions between two
excitons can result in the formation of bound quasiparticles, known as biexcitons.
He used a clever optical trick to observe intervalley biexcitons that comprise two
excitons from different valleys. These novel quasiparticles have no analogue in
conventional semiconductors. Dr. Sie also managed to observe a new type of
optical Stark effect in monolayer WS2, one that is mediated by such intervalley
biexcitons under a blue-detuned driving with circularly polarized light. At higher
excitation densities, many-body interactions between excitons are expected to lead
to several other phenomena that have been quite challenging to observe in conven-
tional semiconductors. Dr. Sie found in monolayer WS2 that the exciton resonance
energy exhibits a pronounced redshift followed by an anomalous blueshift at
increasing exciton density. This observation reveals an attraction-repulsion cross-
over of interactions between excitons, which mimics the well-known Lennard-
Jones interactions between atoms.
In summary, this thesis provides many key insights into light-matter interactions
in monolayer TMDs. Coherent ultrafast optical spectroscopy was successfully used
to both probe and control excitations in these atomically thin semiconductors.
These results may pave the way for enhanced optical control over the valleytronic
properties in two-dimensional materials.
Massachusetts Institute of Technology Nuh Gedik

Cambridge, MA, USA
Preface
Semiconductors that are thinned down to a few atomic layers can exhibit novel
properties beyond those encountered in bulk forms. Transition-metal
dichalcogenides (TMDs) such as MoS2, WS2, and WSe2 are prime examples of
such semiconductors. They appear in layered structure that can be reduced to a
stable single layer where remarkable electronic properties can emerge. Monolayer
TMDs have a pair of electronic valleys which have been proposed as a new way to
carry information in next-generation devices, called valleytronics. However, these
valleys are normally locked in the same energy level, which limits their potential
use for applications.
This dissertation presents the optical methods to split their energy levels by
means of coherent light-matter interactions. Experiments were performed in a
pump-probe technique using a transient absorption spectroscopy on MoS2 and
WS2 and a newly developed XUV light source for time- and angle-resolved
photoemission spectroscopy (TR-ARPES) on WSe2 and WTe2. Hybridizing the
electronic valleys with light allows us to optically tune their energy levels in a
controllable valley-selective manner. In particular, by using off-resonance circu-
larly polarized light at small detuning, we can tune the energy level of one valley
through the optical Stark effect. At larger detuning, we observe a separate contri-
bution from the so-called Bloch-Siegert effect, a delicate phenomenon that has
eluded direct observation in solids. The two effects obey opposite selection rules,
which enables us to separate the two effects at two different valleys.
Monolayer TMDs also possess a strong Coulomb interaction that enhances
many-body interactions between excitons, both bonding and nonbonding interac-
tions. In the former, bound excitonic quasiparticles such as biexcitons play a unique
role in coherent light-matter interactions where they couple the two valleys to
induce opposite energy shifts. The latter are found to exhibit energy shifts that
vii
viii Preface
effectively mimic the Lennard-Jones interactions between atoms. Through these

works, we demonstrate new methods to optically tune the energy levels of elec-
tronic valleys in monolayer TMDs.
Stanford, CA, USA Edbert Jarvis Sie

Parts of this Thesis Have Been Published in the Following Journal Articles
1. E.J. Sie, C.H. Lui, Y.H. Lee, J. Kong, N. Gedik, Large, valley-exclusive Bloch-
Siegert shift in monolayer WS2, Science 355, 1066–1069 (2017) (pdf)
2. E.J. Sie, J.W. McIver, Y.H. Lee, L. Fu, J. Kong, N. Gedik, Valley-selective
optical Stark effect in monolayer WS2, Nat. Mater. 14, 290–294 (2015) (pdf)
(Cover Story)
3. E.J. Sie, A. Steinhoff, C. Gies, C.H. Lui, Q. Ma, M. R€osner, G. Sch€onhoff,
F. Jahnke, T.O. Wehling, Y.H. Lee, J. Kong, P. Jarillo-Herrero, N. Gedik,
Observation of exciton redshift-blueshift crossover in monolayer WS2, Nano
Lett. 17, 4210–4216 (2017) (pdf)
4. E.J. Sie, C.H. Lui, Y.H. Lee, J. Kong, N. Gedik, Observation of intervalley
biexcitonic optical Stark effect in monolayer WS2, Nano Lett. 16, 7421–7426
(2016) (pdf)
5. E.J. Sie, A.J. Frenzel, Y.H. Lee, J. Kong, N. Gedik, Intervalley biexcitons and
many-body effects in monolayer MoS2, Phys. Rev. B 92, 125,417 (2015) (pdf)
6. E.J. Sie, J.W. McIver, Y.H. Lee, L. Fu, J. Kong, N. Gedik, Optical Stark effect in
2D semiconductors, Proc. SPIE 9835 (Invited Paper), Ultrafast Bandgap Pho-
tonics, 983,518 (2016) (pdf)
ix
Acknowledgments
First and foremost, I would like to thank my advisor, Prof. Nuh Gedik, for his
mentorship and support. He has been a constant source of inspiration since I first
started my graduate studies. In fact, it was even before that. I remember our first
meeting at a conference in Boston, where he presented a real-time image of
crystalline lattice motion, which was an awe-inspiring moment for me. He has
been a tremendous support since day one, when I was given the opportunity to
design and build the extreme ultraviolet (XUV) beamline for ARPES in the lab as
well as the freedom to build the white light setup next to it. His vigor for innova-
tions in time-resolved experiments is always inspiring. Throughout my graduate
studies, he has been a true role model for how to be a good scientist and to search for
answers to questions like “So what?” in a perfectly well-stated manner. I also
learned that “no problem is too small, and no problem is too big.” He gave me
and other group members many opportunities to attend international conferences
with the intention that we could learn how to communicate our findings with new
people and meet fellow scientists in the field. Despite his busy schedule, he always
makes time to discuss with group members regularly through weekly group meet-
ings, bi-weekly subgroup meetings, and individual meetings. Apart from discussing
research, he has been a constant source of encouragement and guidance, chatting
with us about personal matters and our careers. Sometimes, I was left wondering
how one person can do so much in such little time, and can become as quick and
sharp minded as a laser while remaining gentle at all times. I sincerely thank Nuh
for every aspect of my graduate education.
I am very grateful to other members of my thesis committee, Prof. Liang Fu and
Prof. Pablo Jarillo-Herrero. Liang has been my theory advisor; many fundamental
explanations for my experiments are inspired by him. One of the many insightful
wisdoms he imparted to me is that the optical Stark effect can be extended to create
a topologically nontrivial phase of matter in monolayer TMDs. Discussing research
with him has always been exciting and stimulating, not because we know anything
more about the theory, but because he knows very well the reality about what the
experiments can do. Much of the theory I understand was patiently explained to me
xi
xii Acknowledgments
after I visited his office several times. He showed me how to use simple diagrams
and mathematical expressions that capture the essence of physics. Now I remember
to use Cartesian coordinates every time I face spherical harmonics problems.
Pablo has been my academic advisor at MIT, where he regularly checked on my
academic progress throughout my graduate studies. His office is like a holy and
respected temple where I can freely discuss my classes, research progress, and
academic career and seek his guidance. I always remember his words that it is better
to complete tasks one at a time rather than attempting to complete everything at
once. I sincerely thank Pablo for letting me have access to his labs to borrow optics
or to perform sample characterization with his group. Every time I invited his group
members out for lunch or dinner, I always feel grateful to be among such highly
skilled people capable of creating cool devices.
My learning and working experience in Gediklab has been very enjoyable
because of the highly spirited colleagues. I am very grateful to Yihua Wang (now
professor at Fudan University), who taught me “Gediklab 101” when I first joined
the group in August 2011. He constructed the ARPES system in the lab and taught
me how it works and how to use it. I learned how to use SolidWorks from him in
order to accurately design and assemble many ultrahigh vacuum (UHV) appara-
tuses for the new extreme ultraviolet (XUV) beamline in the lab. Since then, it has
become my favorite software to draw three-dimensional figures; some of them
appear in the last chapter of this dissert. David Hsieh (now professor at Caltech) has
always been inspiring, and he introduced me to many interesting material systems.
Timm Rohwer has been a great colleague that I had a real pleasure to work together
with and a good friend to have. He joined the group during my third year, and since
then, we have been working together to set up the XUV beamline for ARPES. He
has an infinite reservoir of energy and motivation, which constantly inspires
me. There is no lab equipment that he cannot fix. Zhanybek Alpichshev has been
a constant source of joy and inspiration in the office. I am very fortunate to share an
office with him. I learn something new almost every time I have a conversation with
him. There is no question that he cannot answer. Joshua Lui (now professor at UC
Riverside) taught me how to clearly write stories worth telling. He gave me very
helpful advice during my transition from a graduate student into a more devoted
professional in a later stage of my career.
I also enjoyed my discussions with former group members James McIver, Alex
Frenzel, Darius Torchinsky, Daniel Pilon, Fahad Mahmood, Byron Freelon, Inna
Vishik, Hengyun Zhou, Mahmoud Ghulman, and Steven Drapcho, as well as with
current group members Ozge Ozel, Changmin Lee, Emre Ergecen, Alfred Zong,
Anshul Kogar, Carina Belvin, Suyang Xu, Nikesh Koirala, Mehmet Yilmaz, Guy
Marcus, and Edoardo Baldini. They are very talented individuals and enjoyable to
work with in the lab. There were many good moments that we shared together,
which enriched my experience as a graduate student at MIT.
Outside our lab, I am very thankful to Prof. Yi-Hsien Lee (now professor at
NTHU, Taiwan) and Prof. Jing Kong for their expertise and generous support to
synthesize the high-quality monolayer TMDs that I used in all of my experiments.
My first encounter with Yi-Hsien in the corridor of MIT Building 13 resulted in a
Acknowledgments xiii
long-lasting friendship and professional collaboration, which I hope will continue

in future. I would like to thank Wenjing Fang, who happens to be the source of all
interesting information surrounding our community. I remember her telling me
about the new thin semiconducting materials that could be synthesized in Jing’s
group with the help from Yi-Hsien. This started my pursuit in studying the
monolayer TMDs. I am very grateful to my wonderful friend and colleague
Qiong Ma from Pablo’s group for being my study buddy over the years. She
shows great, professional enthusiasm at work (and outside), which inspires me to
work harder and be more productive. Every time I have questions regarding
graphene or low-dimensional devices, she has always been the first person I
consulted with, and she usually gave more useful tips beyond my questions. She
is like a living dictionary made of graphene, a strong one that can even hold an
elephant! Everybody knows this is no joke. I also thank Yaqing Bie and Yuan Cao
for being my dinner buddies whenever I have a craving for good food (like every
time). Yaqing, the “Queen of Optics” in Pablo’s group, has always been helpful
every time I wanted to discuss about optics in low-dimensional devices. I also thank
the rest of the people in MIT Building 13, Yafang Yang, Linda Ye, Shengxi Huang,
Yuxuan Lin, Lin Zhou, and Xi Ling (now professor at Boston University), who
have been amazing companions during my graduate studies, as well as in exploring
oriental cuisine. I thank Raga Markely for being my lunch buddy, with whom I can
also share my thoughts about everyday life and career. I also thank Yichen Shen,
Purnawirman, Takuma Inoue, Long Wu, Ken Xuan Wei, Chong-U Lim, and Sang
Woo Jun who joined the PhD program at MIT the same year as me and for our
friendship over the years. I am very grateful to Monica Wolf, who has done a lot
more than being our admin secretary. She took care of everything: travel plans,
reimbursements, lab equipment purchases, employment transition, and the big
celebration for my thesis defense (with the help from Qiong and Ozge).
I would like to thank Christopher Gies and Alexander Steinhoff in the University
of Bremen, Germany, for their immense contributions in the theoretical study of
highly excited monolayer TMDs, presented in Chap. 7. It was a wonderful experi-
ence to collaborate with Chris and Alex, from whom I learned a great deal about the
role of plasma screening in monolayer TMDs.
Throughout the years as a graduate student, there were also other researchers
I often encountered at conferences: Jonghwan Kim, Long Ju, Xiaoxiao Zhang,
Yilei Li, Ziliang Ye, Jan Buss, Akshay Singh, and Shiang Fang. I am very grateful
to know them; they make the conference visits more interesting and fruitful,
because we work in similar fields and we can learn from each other. I am sure I
will see them more often in the future, and I look forward to it.
My very special gratitude goes to my parents for their unconditional love,
support, and wisdom. My mother taught me how to speak, to stand, and to love
one another. My father fixed what my mother had taught me.
Massachusetts Institute of Technology Edbert Jarvis Sie

Cambridge, MA, USA
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Monolayer Transition Metal Dichalcogenides (TMDs) . . . . . . . . . 2
1.1.1 Electronic Band Structure . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.2 Optical Selection Rules . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.1.3 Excitons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2 Time-Resolved Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.1 Coherent Light-Matter Interactions . . . . . . . . . . . . . . . . . . 9
1.2.2 Quasi-equilibrium Dynamics . . . . . . . . . . . . . . . . . . . . . . 9
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2 Time-Resolved Absorption Spectroscopy . . . . . . . . . . . . . . . . . . . . . 13
2.1 Experimental Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.1.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.1.2 Laser Amplifier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.1.3 Optical Parametric Amplifier . . . . . . . . . . . . . . . . . . . . . . 16
2.1.4 White Light Continuum . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2 Data Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.2.1 Kramers-Kronig Analysis . . . . . . . . . . . . . . . . . . . . . . . . 21
2.2.2 Maxwell’s Equations for Monolayer Sample . . . . . . . . . . . 22
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3 Intervalley Biexcitons in Monolayer MoS2 . . . . . . . . . . . . . . . . . . . . 27
3.1 Intervalley Biexcitons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.2 Experimental Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.3 Experimental Results and Discussions . . . . . . . . . . . . . . . . . . . . . 30
3.3.1 Intravalley and Intervalley Scattering . . . . . . . . . . . . . . . . 31
3.3.2 Signature of Intervalley Biexcitons . . . . . . . . . . . . . . . . . . 32
3.4 Time-Resolved Cooling Process . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
xv
xvi Contents
4 Valley-Selective Optical Stark Effect in Monolayer WS2 . . . . . . . . . 37

4.1 Optical Stark Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.1.1 Semiclassical Description . . . . . . . . . . . . . . . . . . . . . . . . 40
4.1.2 Quantum-Mechanical Description . . . . . . . . . . . . . . . . . . 42
4.3 Observation of the Optical Stark Effect . . . . . . . . . . . . . . . . . . . . 44
4.4 Valley Selectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.5 Fluence and Detuning Dependences . . . . . . . . . . . . . . . . . . . . . . 46
4.6 Proposal: Valley-Specific Floquet Topological Phase
in TMDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
4.7 Supplementary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.7.1 Time-Resolved Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.7.2 Polarization-Resolved Spectra . . . . . . . . . . . . . . . . . . . . . 51
4.7.3 Obtaining Energy Shift . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.7.4 Comparison from Semiclassical Theory . . . . . . . . . . . . . . 55
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
5 Intervalley Biexcitonic Optical Stark Effect
in Monolayer WS2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
5.1 Blue-Detuned Optical Stark Effect . . . . . . . . . . . . . . . . . . . . . . . 60
5.3 Experimental Results and Data Analysis . . . . . . . . . . . . . . . . . . . 61
5.4 Intervalley Biexcitonic Optical Stark Effect . . . . . . . . . . . . . . . . . 64
5.4.1 Four-Level Jaynes-Cummings Model . . . . . . . . . . . . . . . . 66
5.5 Perspective: Zeeman-Type Optical Stark Effect . . . . . . . . . . . . . . 68
5.6 Supplementary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
5.6.1 Coherent and Incoherent Optical Signals . . . . . . . . . . . . . 68
5.6.2 Time-Trace Fitting Decomposition Analysis . . . . . . . . . . . 70
5.6.3 Possible Effects Under Red-Detuned Pumping . . . . . . . . . 72
5.6.4 Fitting Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
6 Large, Valley-Exclusive Bloch-Siegert Shift
in Monolayer WS2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
6.1 Bloch-Siegert Shift . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
6.1.1 Semiclassical Description . . . . . . . . . . . . . . . . . . . . . . . . 79
6.1.2 Quantum-Mechanical Description . . . . . . . . . . . . . . . . . . 82
6.3 Observation of the Bloch-Siegert Shift . . . . . . . . . . . . . . . . . . . . 85
6.4 Fluence and Detuning Dependences . . . . . . . . . . . . . . . . . . . . . . 87
6.5 Valley-Exclusive Optical Stark Shift and Bloch-Siegert
Shift . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
6.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
Contents xvii
7 Lennard-Jones-Like Potential of 2D Excitons

in Monolayer WS2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
7.1 Many-Body Interactions in 2D TMDs . . . . . . . . . . . . . . . . . . . . . 94
7.3 Optical Signature of Many-Body Effects . . . . . . . . . . . . . . . . . . . 95
7.3.1 Exciton Redshift-Blueshift Crossover . . . . . . . . . . . . . . . . 96
7.3.2 At Low Density: Plasma Contribution . . . . . . . . . . . . . . . 98
7.3.3 At High Density: Exciton Contribution . . . . . . . . . . . . . . . 99
7.4 Lennard-Jones-Like Potential as an Effective Model . . . . . . . . . . 99
7.5 Chronological Signature of Interactions
in Time-Resolved Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
7.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
7.7 Supplementary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
7.7.1 Microscopic Many-Body Computation . . . . . . . . . . . . . . . 104
7.7.2 Exciton-Exciton Annihilation Effect . . . . . . . . . . . . . . . . . 107
7.7.3 Heat Capacity and Estimated Temperature . . . . . . . . . . . . 108
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
8 XUV-Based Time-Resolved ARPES . . . . . . . . . . . . . . . . . . . . . . . . . 115
8.1 Building a High-Resolution XUV Light Source
for TR-ARPES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
8.1.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
8.1.2 XUV Light Source . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
8.1.3 XUV Monochromator . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
8.1.4 XUV Diagnostic Chamber . . . . . . . . . . . . . . . . . . . . . . . . 122
8.2 Measuring TMDs Using 30 eV XUV TR-ARPES . . . . . . . . . . . . 123
8.2.1 WSe2 Semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
8.2.2 WTe2 Semimetal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
Chapter 1
Introduction
Two-dimensional materials can exhibit novel properties beyond those normally

encountered in the bulk compounds. Most evidently is the change in their electronic
density of states and their increasing susceptibility to a Peierls transition. More
interestingly, a number of fascinating phenomena emerge from two-dimensional
materials. This includes quantum well system with quantized energy levels,
two-dimensional electron gas (2DEG) that can exhibit the integer and fractional
quantum Hall effect, layered materials that demonstrate high-temperature super-
conductors, as well as topological insulators that feature nontrivial metallic states at
the surface while remain insulating on the inside. Some of these material systems
can appear as compounds from multiple different elements with complex lattice
structures while maintaining their quasi-two-dimensionality.
Graphene, a single layer of carbon atoms, is a prime example of such 2D
materials that can exhibit some of the above remarkable properties despite its
very simple structure. The electronic structure of graphene is described by a
massless Dirac fermion at around the Fermi level, with the valence and conduction
© Springer International Publishing AG 2018 1

E.J. Sie, Coherent Light-Matter Interactions in Monolayer Transition-Metal
Dichalcogenides, Springer Theses, https://doi.org/10.1007/978-3-319-69554-9_1
2 1 Introduction
bands touching at a single point [1]. This allows graphene to exhibit extremely high
electron mobility, which is a promising property in developing nanoscale electronic
applications. However, the gapless electronic structure in graphene makes it chal-
lenging to use this material for switchable electronics such as transistors. Various
approaches can be used to open a gap in graphene [2], for example, by placing
graphene above a particular substrate that breaks graphene’s sublattice symmetry.
However, the resulting gap induced this way is reported to be around 100 meV [3],
which is still rather small for practical applications.
Transition metal dichalcogenides (TMDs) comprise a family of II–VI semi-
conductors such as MoS2, WS2, MoSe2, and WSe2. These materials are layered in
structure, from which we can isolate a monolayer of TMDs through mechanical
exfoliation or chemical vapor deposition (CVD) growth method [4, 5]. Monolayer
TMDs have a lattice structure similar to graphene, but, unlike graphene, these
materials possess a semiconducting gap between 1 and 2 eV. The large gap in
this class of materials offers promising electronic applications based on
two-dimensional materials. Recently, a microprocessor based on a 2D semiconduc-
tor (MoS2) has been reported [6]. The device consists of 115 transistors comprising
all basic building blocks that are common to most microprocessors. While this class
of materials could be an important element for the development of future 2D
devices, they are found to have novel electronic and optical properties as we discuss
below.
1.1 Monolayer Transition Metal Dichalcogenides (TMDs)
The properties of monolayer TMDs were first studied through pioneering optical
measurements on monolayer MoS2 by Mak et al. [7] and Splendiani et al.
[8]. Monolayer MoS2 is a one-unit-cell-thick semiconductor with a graphene-like
hexagonal lattice of Mo and S atoms where the S-Mo-S layers are stacked in a
trigonal prismatic arrangement (Fig. 1.1a, b). It is a direct bandgap semiconductor
with an optical energy gap of 1.96 eV (10 K) at K and K0 valleys in the Brillouin
zone and a valence band splitting of 160 meV due to strong spin-orbit coupling
(SOC) (Fig. 1.2). Other monolayer TMDs have similar properties, but the magni-
tudes differ slightly, for example, monolayer WS2 has an optical gap of 2.1 eV at
300 K and a valence band splitting of 400 meV. Monolayer TMDs are promising
material systems for future low-energy electronics because it has a unique spin-
valley coupling and a strong Coulomb interaction.
1.1.1 Electronic Band Structure
In this section, we describe the electronic band structure of monolayer MoS2,

following the theoretical studies by Xiao et al. [9] and Liu et al. [10, 11], but the
1.1 Monolayer Transition Metal Dichalcogenides (TMDs) 3
Fig. 1.1 (a) Unit cell of monolayer 2H-MoS2 in a trigonal prismatic arrangement. This structure
lacks an inversion center. (b) Top view of monolayer 2H-MoS2
Fig. 1.2 Hexagonal Brillouin zone of monolayer MoS2. The band edges from conduction bands
(CB) and valence bands (VB) are located at the K and K0 points
general description should also apply to WS2, WSe2, and MoSe2 monolayers. The
band structure of monolayer MoS2 around the gap is well described by considering
the Mo-d orbitals and S-p orbitals. This material has a unit cell that forms a trigonal
prismatic coordination
around the Mo atom that splits its d orbitals into three
0
groups: A1 ðd z2 Þ, E dxy ; d x2 y2 , and E (dxz, dyz). The mirror symmetry along the z^
direction allows a hybridization between A1 and E orbitals, which constitutes the
gap opening at the K and K0 valleys in the Brillouin zone (Fig. 1.3). In the vicinity
of these symmetry points, the wave function of the bands is described by the
following symmetry-adapted basis functions:
1
jϕc i ¼ jd z2 i, jϕv i ¼ pffiffiffi d x2 y2 id xy ð1:1Þ
2
where |ϕci is the basis for conduction band and |ϕvi for valence band and the sign
denotes the K or K0 valley index. The two-band Hamiltonian of monolayer MoS2
4 1 Introduction
Fig. 1.3 Atomic orbital projection of band structures for monolayer MoS2 from first-principle
calculations, without spin-orbit coupling. Fermi energy is set to zero. Symbol size is proportional
to its contribution to corresponding state. (a) Contributions from Mo-d orbital. (b) Total contri-
butions from p orbitals, dominated by S atoms. (c) Total s orbitals (Figure is obtained from Ref.
[10])
mimics that of graphene because both systems have similar symmetry properties,
except for the gap opening due to the differing on-site potentials between the Mo
and S sublattices and the strong spin-orbit coupling (SOC) originated from the
Mo-d orbitals:
Δ σbz 1
H^ ¼ at kx σbx þ ky σby þ σbz λ s^z ð1:2Þ
2 2
where a is the lattice constant, t the hopping integral, k the wave vector, σb the Pauli
matrices for the two basis functions, Δ the energy gap, 2λ the spin splitting at the top
0
of the valence band caused by the SOC interaction H ¼ λL S (ml ¼ 2, ms ¼ 1/2),
and s^z the Pauli matrices for the electron’s spin.
There are three important features that distinguish monolayer MoS2 from
graphene. First, the resulting electronic structure is described by a massive Dirac
fermion due to the finite gap in the second term. This allows an interband electronic
transition at the K and K0 valleys that can be induced through an optical excitation
in the visible regime. Second, the two valleys possess finite and opposite Berry
curvatures owing to the lack of crystalline inversion symmetry. This gives rise to
distinct optical selection rules, which we will discuss further in the next section.
Third, the SOC contribution in the third term leads to a large spin splitting at the
valence band top (160 meV). Meanwhile, the spin splitting at the conduction band
bottom is negligible in the first-order approximation because it is mostly composed
by dz2 orbital (ml ¼ 0). Its magnitude can be obtained by using a second-order
perturbation from the Mo-d orbitals and a first-order perturbation from the minor
S-p orbitals (ml ¼ 1) [12]. Although the conduction band splitting is much smaller
in magnitude (3 meV in MoS2), it plays an important role in the formation of stable
dark excitons in monolayers WS2 and WSe2 [13]; the splitting is larger
(20–40 meV) and inverted.
1.1.2 Optical Selection Rules
In monolayer TMDs, the two valleys couple differently with left- and right-
circularly polarized light [9, 14–16]. At K valley, optical transition from the valence
band (VB) top to the conduction band (CB) bottom is induced exclusively by left-
circularly polarized light. At K0 valley, the optical transition is induced exclusively
by right-circularly polarized light. Such valley selection rules arise from the
different quantum numbers m associated to the bands at the two valleys
(Fig. 1.4). At K valley, the valence bands are assigned m ¼ 1/2 and +1/2 for the
spin-down and spin-up, respectively, while the conduction bands are assigned
m ¼ 3/2 and 1/2 for the spin-down and spin-up, respectively. Interband transi-
tions from VB to CB can occur through absorption of left-circularly polarized light
(σ ) that carries an angular momentum Δm ¼ 1, where we consider electric
dipole approximation that leaves the spin unchanged. At K0 valley, the quantum
numbers have the opposite signs with respect to the K valley because of time-
reversal symmetry. Hence, interband transition at K0 valley can occur through
absorption of right-circularly polarized light (σ +) with Δm ¼ + 1.
The above description can explain the origin of valley selection rules because the
quantum numbers are given. However, obtaining these quantum numbers is not as
straightforward as the addition of orbital and spin angular momenta in atoms.
Isolated atoms in free space have a full spherical symmetry that allows electron
orbitals to acquire magnetic quantum numbers m ¼ 0, 1, 2, 3, . . .. with no
limit. Meanwhile, the crystal lattice of monolayer TMDs has a space group D13h that
imposes a trigonal symmetry C3 at the K symmetry points, so the linear combina-
tion of atomic orbitals (LCAO) throughout the lattice must conform this symmetry.
This limits the effective quantum numbers m ¼ 0, 1, 2 (modulo 3) that can be
present in the system.
In order to obtain the quantum numbers of the conduction and valence bands, we
must find the eigenvalue γ α (α ¼ c,v) of the C3 rotation on the Bloch functions
C3ψ α ¼ γ αψ α. This should include both the constructing atomic orbitals and the
plane wave component of the Bloch functions, expressed as
1 X iKðrþδÞ
ψ α ðrÞ ¼ pffiffiffiffi e dα ðr R δÞ ð1:3Þ
N R
6 1 Introduction
Fig. 1.4 Optical selection

rules in monolayer MoS2
pffiffiffiδ is the position of Mo atom in the unit cell, dc ¼ dz2 ,

where R isthe lattice vector,
and dv ¼ dx2 y2 id xy = 2. There are two contributions to the eigenvalue, first
the C3 rotation about the center of atomic orbital C3dc ¼ dc and C3dv ¼ ei2π/3dv and
second the change of lattice phase factor eiK r at each lattice site. The eigenvalue
γ α depends on the position of the rotation center ρ, which can be Mo atom, S atom,
or the h position (center of hexagon), as shown in Fig. 1.5 (inset). By using
symmetry analysis of C3 on the above Bloch functions, we can obtain the
eigenvalue:
γ αρ ¼ eiKðC3 δδÞ
1
γ dα ð1:4Þ
where δ is the Mo atom position with respect to the rotation center ρ and γ dα is the
eigenvalue about the center of atomic orbitals [11]. In short, the orbital quantum
number ml is obtained from γ ¼ exp(i2πml/3). The simplest example is given at ρ ¼
Mo(δ ¼ 0) where the lattice phase contribution is zero and hence γ cMo ¼ γ dc ¼ 1 and
γ vMo ¼ γ dv ¼ ei2π=3 . The conduction bands are assigned ml ¼ 0 at K and K0 valleys,
while the valence bands are assigned ml ¼ 1 at K valley and +1 at K0 valley. By
adding the spin contributions ms, we can obtain the total quantum numbers mj of
these bands (Fig. 1.5).
We emphasize that the quantum numbers associated with conduction and
valence bands depend on the choice of rotation center, but the upward optical
transition between the spin-conserving bands remains the same, i.e., Δm ¼ 1 at
K valley and +1 at K0 valley. This is a consequence of the lattice symmetry in
monolayer TMDs that also gives rise to the non-zero and opposite Berry curvatures
at the K and K0 valleys. Berry curvature can be viewed as the self-rotating motion of
the electron wave packet or the orbital magnetic moment, and the opposite Berry
curvatures between the K and K0 valleys give rise to the opposite selection rules at
the two valleys.
Fig. 1.5 The C3 rotation eigenvalues γ c,v [10] and quantum numbers of bands in monolayer MoS2,
specified for different rotation centers ρ¼ Mo, S, and h positions (see inset). The quantum numbers
inside the middle row are shown only for the band edges, i.e., spin-down at K valley and spin-up at
K0 valley.
1.1.3 Excitons
Upon photoexcitation, an electron will occupy the conduction band and leave a hole
in the valence band. They have opposite charges and can attract each other through
Coulomb interaction. This allows a formation of bound quasiparticle called an
exciton. Monolayer TMDs are atomically thin semiconductors; so electronic exci-
tation is confined within 2D structure similar to the situation in quantum wells.
There are two important consequences that differentiate the excitons in this system
and in the bulk. First, there is a strong spatial overlap between the electron and hole
orbitals in the z^ direction due to quantum confinement. Second, the electric field
between the electron and hole pair can penetrate outside the material where
screening is absent (Fig. 1.6a–c). These two features enhance the Coulomb attrac-
tion significantly and result in the large excitonic binding energy of 320 meV in
monolayer TMD WS2 as compared to 50 meV in bulk WS2 [17]. The binding
energies are determined through comparing the series of exciton energy levels
obtained experimentally and theoretically. Note that as the electron-hole separation
8 1 Introduction
Fig. 1.6 Interactions between electron and hole that form an exciton are mediated by Coulomb
attraction. (a) In bulk, the electric field is screened by the surrounding material. (b) In monolayer,
large fraction of the electric field penetrates outside the material into the vacuum where screening
is absent or to an appropriate substrate where screening can be varied. (c) The suppressed
screening in monolayer leads to a larger exciton binding energy with respect to the bandgap
(Figures are adapted and redrawn from Ref. [17])
increases, a larger amount of electric field between them penetrates outside the
material and the overall screening gets suppressed. This leads to a pronounced
deviation from the usual hydrogenic series of exciton energy levels.
The optical selection rules in the previous section are discussed in terms of
one-particle picture where Coulomb interaction between the electron and hole pair
is ignored. Note that the selection rules result from the symmetry properties in
monolayer TMDs. Since Coulomb interaction appears as 1/r with a full spherical
symmetry, the symmetry properties in monolayer TMDs are unaffected. Thus,
novel selection rules at the two valleys are maintained, and excitons can be created
in a valley-selective manner using circularly polarized light.
1.2 Time-Resolved Spectroscopy
Monolayer TMDs have a pair of electronic valleys (K and K0 ) whose index can be
used as a new degree of freedom for next-generation valleytronics. Owing to the
optical selection rules, we can use left-circularly polarized light to promote charge
carriers at K valley to carry information with valley index of 1. However, since
the two valleys are energetically degenerate, these carriers can scatter from K valley
to K0 valley and carry the incorrect valley index of +1 (Fig. 1.7). Such intervalley
scattering introduces a valley index mixture throughout propagation until the
population between the two valleys reaches equilibrium. In order to use the valley
index for practical valleytronic devices, it is desirable to suppress the intervalley
scattering. There are two methods to follow up on this line: (1) split the energy
levels between the two valleys, and (2) identify the dominant intervalley scattering
mechanisms and suppress its scattering rate. In our approach, we use light-matter
interactions in a time-resolved manner to achieve this.
1.2 Time-Resolved Spectroscopy 9
Fig. 1.7 Intervalley

scattering of charge carriers
from K valley to K0 valley
1.2.1 Coherent Light-Matter Interactions
Hybridizing light with electrons in materials can result in newly created photon-
dressed states or Floquet states with energy levels that are modified from their
original states. An effective hybridization can be achieved in materials that are
subject to a coherent light field so there exists a phase correlation between the
induced polarization and the incident light. Hence, the resulting hybrid quasiparti-
cle, when written using Bogoliubov transformation, can maintain well-defined
amplitude and energy. This is in a similar situation with the forced harmonic
oscillator, where the interaction energy is transferred periodically between light
and electrons in materials without energy loss. In practice, energy loss can occur
through incoherent interactions. This could be mediated by dissipative scattering
channels upon absorption of resonance light.
In order to suppress the absorption process, we use coherent light source (laser)
that is tuned off-resonance with the material system. Coherent interactions with
off-resonance light can be used to shift the energy levels of materials. As we will
discuss in later chapters, the energy shift (often called the “light shift”) can occur
through two mechanisms, the optical Stark shift and the Bloch-Siegert shift. These
processes can be used to split the energy level between the two valleys using
circularly polarized light that breaks time-reversal symmetry. This optical tech-
nique can offer a much larger energy splitting as compared to that of magnetic field.
1.2.2 Quasi-equilibrium Dynamics
In monolayer TMDs, excitons can be created at a specific valley and switched to the
other valley through intervalley scattering. The lifetime of this scattering process
can be measured using pump-probe spectroscopy, which can occur in
subpicosecond timescale. In this experiment, a left-circularly polarized pump
pulse is used to create excitons at K valley and no excitation at K0 valley. After
some time delay, exciton populations at K and K0 valleys are monitored using left-
and right-circularly polarized probe pulse. The intervalley scattering process can be
10 1 Introduction
measured through the increasing bleaching signal at K0 valley in time-resolved

absorption spectroscopy or through the decreasing polarization rotation of the probe
pulse in time-resolved Faraday or Kerr spectroscopy. The obtained scattering
lifetime can be scrutinized through its dependencies in temperature, charge doping,
spin-orbit coupling strength, exciton density, and substrates. As such, the dominant
intervalley scattering mechanism can be identified, and the scattering rate can be
suppressed.
Mutual interactions between excitons can also be probed using time-resolved
spectroscopy. In later chapters, we will discuss the bound state of two excitons,
called biexciton, which can be induced using two-step excitation. Two excitons that
are created at two different valleys can form an intervalley biexciton, which possess
a unique combination of orbital, spin, and valley degree of freedoms, with no
analogue in atomic systems. Nonbonding interactions between two separate exci-
tons can also occur through atom-like van der Waals interactions. Unlike atoms,
however, excitons usually have much smaller binding energies and can break into
free electron-hole pairs or plasma. This introduces complexities to nonbonding
interactions between excitons in conventional semiconductors. Monolayer TMDs,
on the other hand, provide a special platform for exploring quasiparticle interac-
tions because of their unique two-dimensionality and strong Coulomb interactions,
which render these quasiparticles stable at room temperature. This should allow
more in-depth studies of such interactions at higher excitation density regime that
was previously unexplored in conventional semiconductors.
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two-dimensional semiconductor. Nat. Commun. 8, 14948 (2017)
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semiconductor. Phys. Rev. Lett. 105, 136805 (2010)
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Chapter 2
Time-Resolved Absorption Spectroscopy
This dissertation work emphasizes on the exciton energy shift that is induced by
femtosecond light pulses. At equilibrium, the exciton energy level in monolayer
TMDs sits in the visible regime, e.g., E0 ¼ 2 eV in monolayer WS2. In order to
detect this energy shift, we need a broadband probe pulse that is centered in the
visible spectrum. White light continuum generation is a nonlinear optical process
capable of producing such broadband light pulse between 500 and 700 nm
(hω ¼ 1.8 2.4 eV). In this chapter, we will discuss about time-resolved absorption
spectroscopy setup (or simply transient absorption) that utilizes white light con-
tinuum to probe the exciton energy shift in monolayer TMDs. In the first section, we
will show the overview of the transient absorption setup. In later sections, we will
discuss in more details about (1) laser amplifier, (2) optical parametric amplifier,
© Springer International Publishing AG 2018 13

E.J. Sie, Coherent Light-Matter Interactions in Monolayer Transition-Metal
Dichalcogenides, Springer Theses, https://doi.org/10.1007/978-3-319-69554-9_2
14 2 Time-Resolved Absorption Spectroscopy
and (3) white light continuum generation. Finally, we will discuss about the data
analysis based on the optical physics of monolayer materials on a transparent
substrate.
2.1 Experimental Setup
2.1.1 Overview
Transient absorption spectroscopy consists of synchronized pump pulses and

broadband probe pulses to monitor the pump-induced absorption of materials.
Light has three properties, namely, photon energy, polarization, and intensity,
that, when tuned precisely, can induce various nonequilibrium phenomena in
materials. Examples are resonant excitation of quasiparticles, off-resonance
shifting of energy levels, and valley-selective light-matter interaction. For this
reason, a transient absorption setup can incorporate different stages of light man-
agement area on the optical table to generate light pulses with different photon
energies and to control their polarizations and intensities before reaching the
sample.
The overview of this transient absorption setup is schematically drawn in
Fig. 2.1. In this setup, we use a Ti/sapphire laser amplifier producing laser pulses
with duration of 50 fs and at 30 kHz repetition rate. Each pulse is split into two
arms. For the pump arm, the pulses are sent to an optical parametric amplifier
(OPA) to generate tunable photon energies and modulated by an optical chopper,
while for the probe arm, the pulses are sent through a delay stage and a white light
continuum generator. The pump and probe polarizations are varied separately by
two sets of polarizers and quarter-wave plates, allowing us to perform polarization-
dependent measurements, and an additional half-wave plate for tuning the pump
pulse intensity. The two beams are focused at the sample, and the probe beam is
reflected to a monochromator and a photodiode for lock-in detection. The optical
chopper is externally triggered at 7.5 kHz by the 30 kHz laser amplifier. Here, in
every optical modulation cycle, two adjacent pump pulses are passed, and the next
two adjacent pump pulses are blocked by the optical chopper. By scanning the
grating and the delay stage, we are able to measure induced reflection ΔR/R (hence
induced absorption Δα) as a function of energy and time delay.
2.1.2 Laser Amplifier
One important aspect to consider when setting up a transient absorption setup is the
laser pulse energy. White light continuum generation is a nonlinear optical process
that requires femtosecond pulse energy of 3–5 μJ when using a transparent
nonlinear medium such as a sapphire glass. Although this requirement is easily
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The Viceroy’s Memorial is chiefly interesting as an example of that
chief and unalterable sentiment which actuates the Chinese literati
and has been one of the strongest pillars of Manchu rule, namely,
that the Emperor is infallible, a sentiment based on the fact that
complete and unquestioning loyalty to the Throne is the essential
cornerstone of the whole fabric of Confucian morality, filial piety, and
ancestral worship. While deprecating the Imperial folly, the Viceroy is
therefore compelled to ascribe it to everyone but Her Majesty, and to
praise the Imperial wisdom and benevolence.
His Memorial is as follows:—
“The present war is due to bandits spreading slaughter and

arson on the pretext of paying off a grudge against
Christianity; thus we are face to face with a serious crisis. The
Powers are uniting to send troops and squadrons to attack
China on the plea of protecting their subjects and suppressing
this rebellion. Our position is critical and the provinces are
naturally bound to look now to their defences. I have already
made the necessary preparations, so that if those hordes of
foreigners do invade us, we shall resist them with all our
might. I feel that our Sovereigns are displaying glorious virtue
and that your Majesties are as bountiful as the Almighty. Your
indulgence to the men from afar indicates the boundless
magnanimity and good faith which animate all your actions.
“At present, the first essential is to make the Throne’s
embarrassments, which have led up to the present situation,
widely known, as well as the quality of consistent kindness
with which you are imbued. By so doing, rebels will be
deprived of any pretext for further rioting.
“At the beginning of the war, my colleagues and I issued a
proclamation bidding the people go about their avocations as
usual, and not to give heed to suspicious rumours. A petition
has now reached me from Chinese residents abroad to urge
effective protection for foreigners in China, so that there may
be no risk of revenge being taken on themselves. The
language used is very strong, and we have taken advantage
of the visit of the foreign Consuls, who suggested certain
measures for the protection of missionaries and merchants, to
give orders to the Shanghai Taotai to come to an arrangement
with them in regard to the preservation of peace in the
Yangtsze valley, and at Soochow and Hangchow. This
arrangement will hold good so long as they do not invade the
region in question. The Consuls have telegraphed to their
respective Governments, and I to our Ministers abroad,
explaining fully this arrangement. The Germans, owing to the
murder of their Minister, were disposed to oppose it, but
finally, under compulsion from their colleagues, gave their
consent also.
“I respectfully quote your Majesties’ decree of the 29th of
the 5th Moon (June 25th): ‘The foreign Ministers are now in a
desperately dangerous position; we are still doing our best to
protect them.’ The decree proceeds to direct us to guard well
our respective provinces and to take such steps as policy may
dictate at this emergency. Again, on the 3rd of the 6th Moon
(June 29th), your decree to our Ministers abroad states ‘We
are now sending troops to protect the Legations, but we are
weak and can only do our best. You are to carry on the
business of your missions abroad as usual.’
“In other words, the Throne is inflicting stern and exemplary
punishment on those foreigners in Tientsin who provoked
hostilities, while doing its utmost to protect those innocent
foreign officials, merchants and missionaries who were not
responsible for those attacks. Your benevolence and the
majesty of your wrath are displayed simultaneously,
manifested as brightly as the sun and moon.
“We have again and again implored you to protect the
foreign Ministers: this is the one all-important step which must
on no account be deferred a day, not only because your
Majesties’ own anxiety recognises its necessity, but because
the crisis now forces it upon you.
“The Ministers abroad, Yang Ju and his colleagues, have
telegraphed to the effect that our first duty is to protect the
lives of the foreign Ministers and of all foreigners in China. I
therefore humbly ask you to send competent troops to protect
the Legations in Peking, and by so doing to protect the lives
of your own Envoys abroad. I also urge you to instruct the
provincial authorities to protect all foreigners within their
respective jurisdictions, and thereby to protect our Chinese
subjects residing in foreign lands. My anxiety is intense.”
To this memorial Tzŭ Hsi replied, by express courier and telegram,

as follows:
“Your memorial has reached us. The Throne was reluctant

lightly to enter upon hostilities, as we have already informed
the several foreign Governments and the various provincial
authorities. We have also issued several decrees ordering
protection for the Ministers and foreign residents all over
China. Hence our ideas seem to be identical with your own.
[101] Happily all the Ministers, except Baron von Ketteler, are
perfectly well and quite comfortable; only a day or two ago we
sent them presents of fruits and viands, in order to show our
commiseration. If the Powers now dare to invade your
provinces, you must all protect your territories and resist with
all your might. Even though at the moment peace may prevail,
you must make most strenuous preparations against possible
emergencies. In a word, we will not willingly be the
aggressors. You are to inform our various Legations abroad of
our calm and kindly feelings towards all foreigners, so that
they may think out some plan of a peaceful settlement, in the
general interest. It is highly desirable that you give no ready
ear to vague rumours which are calculated only to lead to
further lack of unity. This decree is to be conveyed by special
courier, at six hundred li (two hundred miles) a day.”
A few days before this Decree, i.e., on the 1st of July, Her Majesty
had drafted with her own pen an explanatory decree for the
edification of the foreign Powers, recounting how the Throne had
been led into its present unpleasant situation. It is interesting to note
that, ten days before, she had offered rewards for the heads of
foreigners in Peking and had sent orders to Yü Hsien to kill every
foreigner in Shansi, which he did. But Tzŭ Hsi had studied her
classics and knew from her own experience how easily dissension
and jealousies could be created among the barbarians.
“Owing to a succession of most unfortunate circumstances,

rapidly and confusedly following each other, we are utterly at
a loss to account for the situation which has brought about
hostilities between China and the Powers. Our
representatives abroad are separated from us by wide seas,
and besides have no special knowledge of the facts, and they
are therefore unable to explain to the respective Foreign
Offices the real state of the Chinese Government’s feelings.
We therefore desire now to place before you the following
detailed statement of the facts.
“In the Provinces of Chihli and Shantung there has arisen a
certain class of disorderly characters who, in their respective
villages, have been wont to practise the use of the quarter-
staff and pugilism, combining these exercises with certain
magic arts and incantations. Owing to the failure of the local
Magistrates to detect and stop these proceedings, the result
has been that gradually a state of unrest has shown itself
throughout that region until, all of a sudden, the Boxer
movement assumed serious proportions. They spread even to
Peking, where they were regarded as possessed of
supernatural powers, so that they gained vast numbers of
followers and universal sympathy. Following in their train the
disorderly people of the lower sort raised a cry of ‘Death to
the Christians!’ following upon which, in the middle of the 5th
Moon, they proceeded to carry their words into deeds, and to
slaughter the converts. The churches were burned, the whole
city was in an uproar, and the population passed completely
out of our control.
“When the first rumours of the coming disaster were noised
abroad, the Legations asked our consent to bring up special
guards, which consent, in view of the special necessities of
the case, was readily given. In all some five hundred foreign
troops came to Peking, which in itself shows plainly the
friendly disposition of the Throne towards all foreign nations.
Under ordinary circumstances the foreign Legations and their
guards do not come in contact with the local Chinese
authorities, and have no relations with them, friendly or
otherwise; but since the arrival of these troops, the soldiers
have not confined themselves to the duty of protecting the
Legations, but have gone upon the city walls and have even
patrolled the outlying parts of the capital, with the result that
shots have been exchanged and blood has been shed.
Indeed, so great are the liberties which they have taken in the
course of their walks abroad, that on one occasion they
actually endeavoured to force their way into the Forbidden
City, which, however, they failed to do. For these reasons
great and widespread indignation has been excited against
them, and evil-doers have seized the opportunity to commit
deeds of slaughter and arson, waxing daily bolder. At this
stage the Powers endeavoured to bring up[102]
reinforcements from Tientsin, but these were cut to pieces on
their journey from the sea, and the attempt was perforce
abandoned. By this time the rebels in the two provinces had
become so intermingled with the people that it was impossible
to identify them. The Throne was by no means averse to give
orders for their suppression, but had we acted with undue
haste, the result might have been a general conflagration, and
our efforts to protect the Legations might have ended in a dire
calamity. If we had proceeded to destroy the rebels in the two
provinces, no single missionary or native Christian would
have been left alive in either, so that we had to proceed
cautiously in this dilemma.
“Under these circumstances we were compelled to suggest
the temporary withdrawal of the Legations to Tientsin, and we
were proceeding to make the necessary arrangements to this
end when the German Minister was unfortunately murdered
one morning on his way to the Tsungli Yamên. This incident
placed the rebel leaders in a desperate position, like that of
the man who rides a tiger and who hesitates whether it be
more dangerous for him to continue his ride or to jump off. It
became then inexpedient that the proposed withdrawal of the
Legations to Tientsin should proceed. All we could do we did,
which was to enforce urgent measures for the due protection
of the Legations in every emergency. To our dismay, on the
16th ultimo, certain foreign naval officers from the squadron
outside Taku had an interview with the Commandant of the
forts, demanding their surrender, and adding that, if their
demand were refused, they would take them by force on the
following day. The Commandant was naturally unable to
betray the trust confided to him, and the foreigners
accordingly bombarded the forts and captured them after a
vigorous resistance. A state of war has thus been created, but
it is none of our doing; besides, how could China be so utterly
foolish, conscious as she is of her weakness, as to declare
war on the whole world at once? How could she hope to
succeed by using the services of untrained bandits for any
such a purpose? This must be obvious to the Powers.
“The above is an accurate statement of our situation,
explaining the measures unavoidably forced upon China to
meet the situation. Our representatives abroad must carefully
explain the tenor of this decree to the Governments to which
they are accredited. We are still instructing our military
Commanders to protect the Legations, and can only do our
best. In the meantime you, our Ministers, must carry on your
duties as usual, and not pose as disinterested spectators.”
Supplementing this Decree, the Empress, possibly instigated by

some of the master-minds of the Grand Council, proceeded to
prepare the way for a time-honoured, and invariably successful,
device of Chinese statecraft, namely, the creation of dissension and
jealousy between the Powers, and to this end she addressed
telegrams to the Emperor of Russia, Queen Victoria, the Emperor of
Japan, and other rulers. It is typical of the infantile naïveté of
Chinese officials in such matters of foreign policy, that copies of
these extraordinary messages, intended solely to mislead public
opinion abroad, should have been sent in to the (still besieged)
Legations with the cards of Prince Ch’ing, and the Ministers of the
Tsungli Yamên.[103] It is certain that these artless telegrams, as well
as the conciliatory instructions subsequently sent to China’s
representatives abroad, were but the outward and visible signs of
Tzŭ Hsi’s inward and spiritual misgivings caused by the fall of the
Taku Forts, the capture of the native city of Tientsin, and the massing
of the armies of the Allies for the advance on her capital. If possible,
she would therefore make friends in advance among the humane,
and invariably gullible, sovereigns of Europe, making good use of
her knowledge of their little weaknesses in matters of foreign policy,
and be ready to pose in due course as the innocent victim of
circumstance and fate. But “in the profound seclusion of her Palace”
she continued to hope against hope for the Boxers’ promised
victories and the fall of the Legations which she was so carefully
“protecting.”
And here let us briefly digress. Students of modern Chinese
history, desirous of applying its latest lessons to future uses, will no
doubt observe, that in advising the Throne either for peace or war, all
Chinese and Manchu officials (no matter how good or bad from our
point of view, how brave or cowardly, how honest or corrupt) agree
and unite in frankly confessing to their hatred of the foreigner and all
his works. This sentiment, loudly proclaimed by the simple-minded
braggart Boxers, is politely re-echoed by the literati, and voiced with
equal candour by the picked men of the Government, men like Yuan
Shih-k’ai, Jung Lu, and Liu K’un-yi. Those who pose as the friends of
foreigners merely advocate dissimulation as a matter of expediency.
The thought should give us pause, not only in accepting at their
current value the posturings and pronouncements of the monde
diplomatique at Peking, and the reassurances given as to our
excellent relations with such-and-such officials, but it should also
lead us to consider what are the causes, in us or in them, which
produce so constant and so deep a hatred? If we study the
Memorials of high Chinese officials for the past fifty years, the same
unpleasant feature presents itself at every turn. We may meet with
exceptional cases, here and there, like Yüan Ch’ang, who will
profess respect for the European, but even his respect will be
qualified and never go to the length of intimate friendship. Our
perennial gullibility, that faculty which makes the Chinese classical
“allurements” invariably successful with the foreigner, accounts, no
doubt, to some extent for the Chinese official’s contempt for our
intelligence, and for our failure to learn by experience. It is fairly
certain that the Boxers of to-morrow will be pooh-poohed (if not
applauded) in advance by our Chinese Secretariats, as they were in
1900. But for the Chinese official’s unchanging hostility towards us,
no such explanation offers, and it is perhaps, therefore, most
satisfactory to our amour propre to assume that his attitude is
dictated by feelings similar to those which inspired Demetrius of the
Ephesians, ostensibly fearful for the cult of Diana, but in reality
disturbed for his own livelihood.
To return. The following are translations of the telegrams sent
under date 3rd July, by order of the Empress Dowager, to the
Emperor of Russia, Queen Victoria, and the Emperor of Japan. The
text of those which were sent at the same time to the Presidents of
the French and American Republics, and which were dated,
curiously enough, on the 19th of June (the Taku Forts fell on the
16th), have been published in Monsieur Cordier’s most accurate and
painstaking work, Les Relations de la Chine, Vol. III.
Telegram dated 3rd July:—
“To the Emperor of Russia:—Greeting to your Majesty! For

over two hundred and fifty years our neighbouring Empires
have enjoyed unbroken relations of friendship, more cordial
than those existing between any other Powers.
“Recent ill-feeling created between converts to Christianity
and the rest of our people have afforded an opportunity to
evil-disposed persons and rebels to create disturbances, and
the result has been that the foreign Powers have been led to
believe that the Throne itself is a party to their proceedings
and is hostile to Christianity. Your Majesty’s representative at
my Court (M. de Giers) has actually requested our Foreign
Office to suppress the rebellion and thus to allay the
suspicions of the Powers. But at the time that he made this
request, Peking was thoroughly infested with rebels, who had
stirred up the people and gained for themselves no small
prestige. Not only our soldiery but the mass of the people
were burning for revenge against those who practised the
foreign religion, and even certain Princes of our Imperial Clan
joined in the movement, declaring that there was no room in
the Celestial Kingdom for Christianity and the ancient
religions of the soil. My chief anxiety has been lest any
precipitate action on the part of the Government might lead to
some dire catastrophe (i.e., the destruction of the Legations),
and I feared, too, that the anti-foreign movement might break
out simultaneously at the Treaty Ports in the South, which
would have made the position hopeless. I was doing my
utmost to find a way out of the dilemma when the foreign
Powers, evidently failing to realise the difficulties of our
situation, precipitated matters by the bombardment and
capture of the Taku Forts: now we are confronted with all the
dire calamities of war, and the confusion in our Empire is
greater than ever before. Amongst all the Powers, none has
enjoyed such friendly relations with China as Russia. On a
former occasion I deputed Li Hung-chang to proceed to your
Majesty’s capital as my special Envoy; he drew up on our
behalf and concluded with your country a secret Treaty of
Alliance, which is duly recorded in the Imperial Archives.
“And now that China has incurred the enmity of the civilised
world by stress of circumstances beyond our power to control,
I must perforce rely upon your country to act as intermediary
and peacemaker on our behalf. I now make this earnest and
sincere appeal to your Majesty, begging that you may be
pleased to come forward as arbitrator, and thus to relieve the
difficulties of our situation. We await with anxiety your
gracious reply.”
On the same day the Empress Dowager addressed Her Majesty

Queen Victoria in a telegram which was sent in the Emperor’s name
and forwarded through the Chinese Minister in London. Its text runs
as follows:—
“To your Majesty, greeting!—In all the dealings of England

with the Empire of China, since first relations were
established between us, there has never been any idea of
territorial aggrandisement on the part of Great Britain, but only
a keen desire to promote the interests of her trade. Reflecting
on the fact that our country is now plunged into a dreadful
condition of warfare, we bear in mind that a large proportion
of China’s trade, seventy or eighty per cent., is done with
England: moreover, your Customs duties are the lightest in
the world, and few restrictions are made at your sea-ports in
the matter of foreign importations; for these reasons our
amicable relations with British merchants at our Treaty Ports
have continued unbroken for the last half century, to our
mutual benefit.
“But a sudden change has now occurred and general
suspicion has been created against us. We would therefore
ask you now to consider that if, by any conceivable
combination of circumstances, the independence of our
Empire should be lost, and the Powers unite to carry out their
long plotted schemes to possess themselves of our territory,
the results to your country’s interests would be disastrous and
fatal to your trade. At this moment our Empire is striving to the
utmost to raise an army and funds sufficient for its protection;
in the meanwhile we rely upon your good services to act as
mediator, and now anxiously await your decision.”
Again, in the name of the Emperor and through the Chinese
Minister at Tokio, the following message was addressed to the
Emperor of Japan:—
“To your Majesty, greeting!—The Empires of China and

Japan hang together, even as the lips and the teeth, and the
relations existing between them have always been
sympathetic. Last month we were plunged in deep grief when
we learned of the murder of the Chancellor of your Legation in
Peking; we were about to arrest and punish the culprits when
the Powers, unnecessarily suspicious of our motives, seized
the Taku Forts, and we found ourselves involved in all the
horrors of war. In face of the existing situation, it appears to
us that at the present time the Continents of Europe and Asia
are opposed to each other, marshalling their forces for a
conflict of irreconcilable ambitions; everything therefore
depends upon our two Asiatic Empires standing firm together
at this juncture. The earth-hungry Powers of the West, whose
tigerish eyes of greed are fixed in our direction, will certainly
not confine their attention to China. In the event of our Empire
being broken up, Japan in her turn will assuredly be hard
pressed to maintain her independence. The community of our
interests renders it clearly imperative that at this crisis we
should disregard all trifling causes of discord, and consider
only the requirements of the situation, as comrade nations.
We rely upon your Majesty to come forward as arbitrator, and
anxiously await your gracious reply to this appeal.”
These remarkable effusions have been inscribed in the annals of

the Dynasty, by order of Her Majesty, those same annals from which
all her Boxer Edicts have been solemnly expunged for purposes of
historic accuracy. One cannot but hope that, in process of time,
consideration of facts like these may cure European diplomacy and
officialdom generally of its unreasoning reverence for the Chinese
written character, a species of fetish-worship imbibed from the native
pundit and aggravated by the sense of importance which knowledge
of this ancient language so frequently confers.
These Imperial messages throw into strong relief the elementary
simplicity of China’s foreign policy, a quality which foreigners
frequently misunderstand, in the general belief that the Oriental mind
conceals great depths of subtlety and secret information. Looking at
these documents in the light of the known facts of China’s political
situation at that moment, and stripping them of all artificial glamour, it
becomes almost inconceivable that any Government should publish
to the world and file in its archives such puerile productions. But it is
frequently the case that this very kindergarten element in Chinese
politics is a stumbling-block to the elaborate and highly specialised
machinery of European diplomacy, and that, being at a loss how to
deal with the suspiciously transparent artifices of the elderly children
of the Waiwupu, the foreigner excuses and consoles himself by
attributing to them occult faculties and resources of a very high
order. If one must be continually worsted, it is perhaps not unwise to
attribute to one’s adversary the qualities of Macchiavelli, Talleyrand
and Metternich combined. As far as British interests are concerned,
one of the chief lessons emphasised by the events of the past ten
years in China is, that the reform of our diplomatic machinery (and
particularly of the Consular service) is urgently needed, a reform for
which more than one British Minister has vainly pleaded in Downing
Street.
XX
THE FLIGHT FROM PEKING AND THE COURT IN
EXILE
The diarist, Ching Shan, has described in detail the flight of the
Empress Dowager and Emperor from Peking, before dawn, on the
morning of the 15th August. From an account of the Court’s journey,
subsequently written by the Grand Secretary, Wang Wen-shao, to
friends in Chekiang, and published in one of the vernacular papers of
Shanghai, we obtain valuable corroboration of the diarist’s accuracy,
together with much interesting information.
Wang Wen-shao overtook their Majesties at Huai-lai on the 18th
August; for the past three days they had suffered dangers and
hardships innumerable. On the evening of the 19th they had stopped
at Kuanshih (seventy li from Peking), where they slept in the
Mosque. There the Mahommedan trading firm of “Tung Kuang yü”
(the well-known contractors for the hire of pack animals for the
northern caravan trade) had supplied them with the best of the poor
food available—coarse flour, vegetables, and millet porridge—and
had provided mule litters for the next stage of the journey. As the
troops of the escort had been ordered to remain at some distance
behind, so long as there was any risk of pursuit by the Allies’ cavalry,
their Majesties’ arrival was unannounced, and their identity
unsuspected. As they descended from their carts, travel-stained,
weary, and distressed, they were surrounded by a large crowd of
refugee idlers and villagers, eager for news from the capital. An eye-
witness of the scene has reported that, looking nervously about him,
the Emperor said, “We have to thank the Boxers for this,” whereupon
the Old Buddha, undaunted even at the height of her misfortunes,
bade him be silent.
Next day they travelled, by mule litter, ninety li (thirty-two miles),
and spent the night at Ch’a-Tao, just beyond the Great Wall. Here no
preparations of any kind had been made for their reception, and they
suffered much hardship, sleeping on the brick platform (k’ang)
without any adequate bedding. But the Magistrate of Yen-Ch’ing
chou had been able to find a blue sedan-chair for Her Majesty, who
had thus travelled part of the day in greater comfort. Also at midday,
stopping to eat at Chü-yung kuan, Li Lien-ying, the chief eunuch, had
obtained a few tea cups from the villagers.
On the 16th they travelled from Ch’a-Tao to Huai-lai, a hard stage
of fifty li. Some of the officials and Chamberlains of the Court now
joined their Majesties, so that the party consisted of seventeen carts,
in addition to the Old Buddha’s palanquin and the Emperor’s mule
litter. As the cortège advanced, and the news of their flight was
spread abroad, rumours began to be circulated that they were
pretenders, personating the Son of Heaven and the Old Buddha,
rumours due, no doubt, to the fact that Her Majesty was still wearing
her hair in the Chinese manner, and that her clothes were the
common ones in which she had escaped from the Forbidden City. In
spite of these rumours the Magistrate of Huai-lai, a Hupeh man (Wu
Yung), had received no intimation of their Majesties’ coming, and,
when the Imperial party, accompanied by an enormous crowd,
entered his Yamên, he had no time to put on his official robes, but
rushed down to receive them as he was. After prostrating himself, he
wanted to clear out the noisy and inquisitive rabble, but the Old
Buddha forbade him, saying, “Not so; let them crowd around us as
much as they like. It amuses me to see these honest country folk.”
Here, after three days of coarse fare, the Empress Dowager rejoiced
once more in a meal of birds’-nest soup and sharks’ fins, presented
by the Magistrate, who also furnished her with an outfit of woman’s
clothing and suits for the Emperor and the Heir Apparent, for all of
which he received Her Majesty’s repeated and grateful thanks.
It was here, at Huai-lai, while the Court was taking a day’s rest,
that Wang Wen-shao came up with them. He was cordially, even
affectionately, greeted by the Old Buddha, who condoled with him on
the hardships to which he had been exposed, and insisted on his
sharing her birds’-nest soup, which, she said, he would surely enjoy
as much as she had done after so many and great privations. She
rebuked the Emperor for not greeting the aged Councillor with warm
thanks for his touching devotion to the Throne.
From Huai-lai, Prince Ch’ing was ordered to return to Peking to
negotiate terms of peace with the Allies. Knowing the difficulties of
this task, he went reluctantly; before leaving he had a long audience
with Her Majesty, who assured him of her complete confidence in his
ability to make terms, and bade him adopt a policy similar to that of
Prince Kung in 1860.
Wang Wen-shao’s account of the first part of the Court’s journey is
sufficiently interesting to justify textual reproduction.
“Their Majesties fled from the palace at the dawn of day in

common carts. It was only after their arrival at Kuanshih that
they were provided with litters. The Emperor and Prince P’u
Lun rode on one cart until their arrival at Huai-lai, where the
District Magistrate furnished a palanquin, and later on, at
Hsüan-hua, four large sedan chairs were found for the
Imperial party. It was at this point that the Emperor’s Consort
overtook their Majesties.
“So hurried was the flight that no spare clothes had been
taken; the Empress Dowager was very shabbily dressed, so
as to be almost unrecognisable, the Chinese mode of hair-
dressing producing a very remarkable alteration in her
appearance. On the first night after leaving Peking, they slept,
like travellers of the lowest class, on the raised brick platform
of the inn, where not even rice was obtainable for the evening
meal, so that they were compelled to eat common porridge
made of millet. In all the disasters recorded in history, never
has there been such a pitiful spectacle.
“It was only after reaching Huai-lai that their condition
improved somewhat, but even then the number of personal
attendants and eunuchs was very small, and not a single
concubine was there to wait upon the Old Buddha. For the
first few days’ flight, neither Prince Li, nor Jung Lu, nor Ch’i
Hsiu (all of them Grand Councillors), were in attendance so
that Her Majesty nominated Prince Tuan to serve on the
Council. She reviled him at the outset severely, reproaching
him for the misfortunes which had overtaken the Dynasty, but
as time went on, as he shared with her the privations and
troubles of the day’s journey, she became more gracious
towards him. This was to some extent due to the very great
influence which Prince Tuan’s wife exercised at Court.
“When I reached Huai-lai, the Court consisted of the
Princes Tuan, Ching, Na, Su, and P’u Lun, with a following of
high officials led by Kang Yi, and some twenty Secretaries.
General Ma’s troops and some of the Banner Corps of Prince
Tuan formed the Imperial escort; and they plundered every
town and village on their line of march. This, however, is
hardly remarkable, because all the shops had been closed
and there were no provisions to be purchased anywhere.
“To go back for a few days. Yü Lu (Viceroy of Chihli) shot
himself in a coffin shop at a place south of the Hunting Park,
and Li Ping-heng took poison after the defeat of his troops at
T’ungchow. The Court’s flight had already been discussed
after the first advance of the Allies from T’ungchow towards
Peking; but the difficulty in providing sufficient transport was
considered insuperable. On the 19th of the Moon a steady
cannonade began at about midnight, and, from my house in
Magpie Lane, one could note, by the volume of sound, that
the attack was steadily advancing closer to the city, and
eventually bullets came whistling as thick as hail. The
bombardment reached its height at about noon on the 20th,
when news was brought that two gates of the Imperial City
had been taken by storm. I was unable to verify this report. It
was my turn for night duty at the Palace, but after the last
audience, I was unable to enter the Forbidden City, as all its
gates were barred. It was only at 7 a.m. on the 21st inst.
(August 15th) that I was able to gain admittance to the
Forbidden City, and then I learned that their Majesties had
hurriedly fled. On the previous day five urgent audiences with
the Grand Council had been held; at the last of these only
Kang Yi, Chao Shu ch’iao, and myself were present. Sadly
regarding us, the Old Buddha said, ‘I see there are only three
of you left. No doubt all the rest have fled, leaving us, mother
and son, to our fate. I want you all to come with me on my
journey.’ Turning to me she then said, ‘You are too old. I
would not wish you to share in all this hardship. Follow us as
best you can later on.’ The Emperor expressed his wishes in
the same sense.
“By this time it was nearly midnight, and they still hesitated
about leaving the city; judge then of my surprise to learn that,
at the first streak of dawn, their Majesties had left the city in
indescribable disorder and frantic haste. I could not return to
my house that day because all the gates of the Imperial City
were closed, but at 10 a.m. on the following day, I made my
way out of the Houmen.[104] On my way I came across Jung
Lu; he had fainted in his chair, and had been forsaken by his
cowardly bearers. He said: ‘This is the end. You and I never
believed in these Boxers; see now to what a pass they have
brought the Old Buddha. If you see Her Majesty, tell her that I
have gone to rally the troops, and that, if I live, I will join her
later on.’
“After leaving Jung Lu, I made my way to a little temple
which lies midway between the North and the North-West
Gates of the city, and there I rested a while. It was the opinion
of the Abbot in charge that the foreigners would burn every
temple of the city, as all of them had been used by the Boxers
for their magic rites, and he said that, in times of dire peril
such as this, it was really inconvenient for him to offer any
hospitality to visitors. Just at this moment news was brought
us that the foreign troops were on the wall of the city, between
the two gates nearest to us, and that they were firing down
upon the streets; the city was already invested, but the
foreigners were not molesting civilians, though they were
shooting all ‘braves’ and men in uniform. As the priest
declined to receive me, I sought refuge at the house of a man
named Han, retainer in the Imperial Household, who lived
close by. All my chair-bearers and servants had fled. Shortly
after noon I heard that one might still leave Peking by the Hsi-
chih Men; so leaving everything—carts, chairs, and animals—
where they were, I started off at dusk on foot with such money
and clothing as I had on my person. The road ahead of me
was blocked by a dense crowd of refugees. I took the road by
the Drum Tower, skirting the lakes to the north of the Imperial
City. Towards evening a dreadful thunderstorm came on, so I
took refuge for the night with the Ching family. The
bombardment had ceased by this time, but the whole northern
part of the Imperial City appeared to be in flames, which
broke out in fresh places all through the night. At three in the
morning we heard that the West Gates were opened, and that
the City Guards had fled, but that the foreigners had not yet
reached that part of the city.
“I had intended to travel by cart, but the disorganised troops
had by this time seized every available beast of burden. My
second son, however, was luckily able to persuade Captain
Liu to fetch one of my carts out from the city, and this was
done after several narrow escapes. I had left Peking on foot,
but at the bridge close to the North-West Gate I found this
cart awaiting me, and with it my second son, who was riding
on a mule, and the five servants who remained to us following
on foot. When we reached Hai-Tien (a town which lies close
to the Summer Palace) every restaurant was closed, but we
managed to get a little food, and then hurried on after their
Majesties to Kuanshih, where we passed the night. Next day,
continuing our journey, we learned that their Majesties were
halting at Huai-lai, where we overtook them on the 24th day of
the Moon. We expect to reach T’ai-yüan fu about the middle
of next week.
“The dangers of our journey are indescribable. Every shop
on the road had been plundered by bands of routed troops,
who pretend to be part of the Imperial escort. These bandits
are ahead of us at every stage of the journey, and they have
stripped the country-side bare, so that when the Imperial party
reaches any place, and the escort endeavour to commandeer
supplies, the distress of the inhabitants and the confusion
which ensues are really terrible to witness. The districts
through which we have passed are literally devastated.”
From Huai-lai the Court moved on to Hsüan-hua fu, a three days’

march, and there remained for four days, resting and preparing for
the journey into Shansi. The Border Warden at Sha-ho chên had
provided their Majesties with green (official) sedan chairs, and the
usual etiquette of the Court and Grand Council was being gradually
restored. Her Majesty’s spirits were excellent, and she took a keen
interest in everything. At Chi-ming yi, for instance, she was with
difficulty dissuaded from stopping to visit a temple on the summit of
an adjoining hill, in honour of which shrine the Emperor Kanghsi had
left a tablet carved with a memorial inscription in verse.
At Hsüan-hua fu there was considerable disorder, but the Court
enjoyed increased comforts; thanks to the zeal and energy of the
local Magistrate (Ch’en Pen). Here the Old Buddha received Prince
Ch’ing’s first despatch from Peking, which gave a deplorable account
of the situation.
The Court left Hsüan-hua on the 25th August (its numbers being
increased by the Emperor’s Consort with a few of her personal
attendants) and spent the night at a garrison station called Tso-Wei.
The deplorable state of the country was reflected in the
accommodation they found there; for the guards had fled, and the
official quarters had all been plundered and burnt, with the exception
of two small rooms, evil-smelling and damp. There was no food to be
had, except bread made of sodden flour. One of the two available
rooms was occupied by the Old Buddha, the other by Kuang Hsü
and his Consort, while all the officials of the Court, high and low,
fared as best they might in the stuffy courtyard. For once the
venerable mother’s composure deserted her. “This is abominable,”
she complained; “the place swarms with insects, and I cannot sleep
a wink. It is disgraceful that I should have come to such a pass at my
time of life. My state is worse even than that of the Emperor Hsüan-
Tsung of the T’ang Dynasty, who was forced to fly from his capital,
and saw his favourite concubine murdered before his very eyes.” An
unsubstantiated report that the Allies had plundered her palace
treasure vaults was not calculated to calm Her Majesty, and for a
while the suite went in fear of her wrath.
On August 27th the Court crossed the Shansi border, and spent
the night at T’ien-chen hsien. The local Magistrate, a Manchu, had
committed suicide after hearing of the fall of Moukden and other
Manchurian cities; and the town was in a condition of ruinous
disorder. Their Majesties supped off a meal hastily provided by the
Gaol Warder. But their courage was restored by the arrival of Ts’en
Ch’un-hsüan,[105] an official of high intelligence and courage, who
greatly pleased the Old Buddha by bringing her a gift of eggs and a
girdle and pouch for her pipe and purse.
On the 30th August the Court lay at Ta-t’ung fu, in the Yamên of
the local Brigadier-General. They stayed here four days, enjoying the
greatly improved accommodation which the General’s efforts had
secured for them.
On September 4th, they reached the market town of T’ai-yüeh,
having travelled thirty-five miles that day, and here again they found
damp rooms and poor fare. But Her Majesty’s spirits had recovered.
On the 16th, while crossing the hill-pass of the “Flighting Geese,”
Her Majesty ordered a halt in order to enjoy the view. “It reminds me
of the Jehol Country,” she said. Then, turning to the Emperor, “After
all, it’s delightful to get away like this from Peking and to see the
world, isn’t it?” “Under happier circumstances, it would be,” replied
Kuang Hsü. At this point Ts’en Ch’un-hsüan brought Her Majesty a
large bouquet of yellow flowers, a present which touched her deeply:
in return she sent him a jar of butter-milk tea.
On the 7th, the only accommodation which the local officials had
been able to prepare at Yüan-p’ing was a mud-house belonging to
one of the common people, in which, by an oversight, several empty
coffins had been left. Ts’en, arriving ahead of the party, was told of
this, and galloped to make excuses to Her Majesty and take her

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Coherent Light-Matter Interactions in

Two Dimensional Transition Metal Dichalcogenides 1st

Transition metal catalyzed furans synthesis :

Transition Metal-Catalyzed Pyridine Synthesis.

Spectral Methods in Transition Metal Complexes 1st

Transition Metal-Catalyzed Benzofuran Synthesis Xiao-

Light-matter interaction : physics and engineering at

Handbook of transition metal polymerization catalysts

Transition Metal Catalyzed Pyrimidine, Pyrazine,

Edbert Jarvis Sie

Recognizing Outstanding Ph.D. Research

Theses are accepted into the series by invited nomination only

More information about this series at http://www.springer.com/series/8790

ISSN 2190-5053 ISSN 2190-5061 (electronic)

Library of Congress Control Number: 2017957976

© Springer International Publishing AG 2018

Printed on acid-free paper

This Springer imprint is published by Springer Nature

comparable to what would be obtained using a magnetic field of ~100 Tesla.

Massachusetts Institute of Technology Nuh Gedik

effectively mimic the Lennard-Jones interactions between atoms. Through these

Stanford, CA, USA Edbert Jarvis Sie

long-lasting friendship and professional collaboration, which I hope will continue

Massachusetts Institute of Technology Edbert Jarvis Sie

4 Valley-Selective Optical Stark Effect in Monolayer WS2 . . . . . . . . . 37

7 Lennard-Jones-Like Potential of 2D Excitons

Two-dimensional materials can exhibit novel properties beyond those normally

© Springer International Publishing AG 2018 1

1.1 Monolayer Transition Metal Dichalcogenides (TMDs)

1.1.1 Electronic Band Structure

In this section, we describe the electronic band structure of monolayer MoS2,

1.1.2 Optical Selection Rules

Fig. 1.4 Optical selection

pffiffiffiδ is the position of Mo atom in the unit cell, dc ¼ dz2 ,

1.2 Time-Resolved Spectroscopy

Fig. 1.7 Intervalley

1.2.1 Coherent Light-Matter Interactions

1.2.2 Quasi-equilibrium Dynamics

measured through the increasing bleaching signal at K0 valley in time-resolved

© Springer International Publishing AG 2018 13

2.1 Experimental Setup

Transient absorption spectroscopy consists of synchronized pump pulses and

2.1.2 Laser Amplifier

“The present war is due to bandits spreading slaughter and

To this memorial Tzŭ Hsi replied, by express courier and telegram,

“Your memorial has reached us. The Throne was reluctant

“Owing to a succession of most unfortunate circumstances,

Supplementing this Decree, the Empress, possibly instigated by

“To the Emperor of Russia:—Greeting to your Majesty! For

On the same day the Empress Dowager addressed Her Majesty

“To your Majesty, greeting!—In all the dealings of England

“To your Majesty, greeting!—The Empires of China and

These remarkable effusions have been inscribed in the annals of

“Their Majesties fled from the palace at the dawn of day in

From Huai-lai the Court moved on to Hsüan-hua fu, a three days’

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