Solution to Problem 16: Circularly Polarized Raman Spectroscopy in MoS₂

For a first-order Raman process the scattered amplitude is

M = P_sᵀ R P_i, I ∝ |M|²,
where R is the Raman tensor of the phonon mode, and P_i, P_s are the circular polarization
vectors of the incident and scattered light, respectively.

For monolayer MoS₂ (point group D₃h) the in-plane Raman-active phonons are divided into
two irreducible representations. Their Raman tensors (in the sample xy-plane) are:

A′₁ : R(A′₁) = [[a 0],

[0 a]]

E′ : R(E′) = [[0 ±d],

[±d 0]]

Left- and right-handed in-plane circular polarizations are defined as

P₊ = (1/√2)[1, i]ᵀ, P₋ = (1/√2)[1, −i]ᵀ.

Channel M(A′₁) I(A′₁) M(E′) I(E′)

Co-circular (P_i 0 0 ±2di 4d²

= P_s)

Cross-circular 2a 4a² 0 0
(P_i ≠ P_s)

Selection-rule summary:

 • A′₁ mode: Allowed only in cross-circular (opposite-handed) configuration; forbidden in

co-circular.
• E′ mode: Allowed only in co-circular (same-handed) configuration; forbidden in
cross-circular.

Thus, recording Raman spectra with parallel (co-circular) and perpendicular

(cross-circular) settings of the polarizer/analyzer cleanly separates the two phonon
symmetries and identifies the chiral E′ phonons.
Problem 16 (b) Analysis of the “Abnormal” Circular‐Polarized Raman Response in
Monolayer MoS₂

In an ideal D₃h-symmetric monolayer MoS₂ the first-order Raman selection rules derived
from the mode tensors are:

• Co-circular (parallel) polarisations (P₊→P₊ or P₋→P₋): only the chiral in-plane E′ mode is
allowed; the A′₁ breathing mode is forbidden.
• Cross-circular (perpendicular) polarisations (P₊→P₋ or P₋→P₊): only the A′₁ mode is
allowed; the E′ mode is forbidden.

Drapcho et al. reported the opposite behaviour: in the perpendicular geometry the E′
intensity remains finite while A′₁ vanishes, and in the parallel geometry both modes appear.
This “forbidden-channel” leakage indicates that the crystal in the experiment no longer
possesses the full in-plane symmetry assumed in the textbook tensor analysis.

Likely Origins of the Symmetry Relaxation

1. **Substrate-induced symmetry breaking (σₕ loss).** Monolayer MoS₂ is supported on
SiO₂/Si in most micro-Raman setups; the substrate removes the out-of-plane mirror plane
and can mix A′ and A″ modes, giving the A′₁ tensor small off-diagonal components that
activate it in co-circular geometry.

2. **Residual strain / rippling.** Non-uniform strain or curvature lowers the three-fold

rotational symmetry (C₃) and allows E′ components to couple to cross-circular light,
explaining the finite E′ signal in the P₋→P₊ configuration.

3. **Finite numerical aperture (NA) and collection of off-axis light.** A high-NA objective
collects scattered light over a distribution of k-vectors; the resulting polarisation vectors
are not perfectly circular in the sample frame, causing an effective mixture of co- and
cross-circular channels.

4. **Small crystal misalignment.** If the basal plane is tilted a few degrees with respect to
the optical axis, z-components of the electric field appear, contributing additional tensor
elements and again relaxing the strict selection rules.

How the “Abnormal” Spectrum Emerges

With any of the above perturbations, the Raman tensors acquire extra elements so that
M′(A′₁) ∝ ε · (P_s^† δR P_i) and M′(E′) ∝ … are no longer zero in the forbidden
combinations.
Consequently:

• **Perpendicular (P₋→P₊):** a small off-diagonal element in the E′ tensor yields a non-zero

E′ intensity, while the corresponding element in A′₁ cancels, keeping A′₁ dark.
• **Parallel (P₊→P₊):** the modified A′₁ tensor now overlaps with the incident/scattered
polarisations, so both A′₁ and E′ appear.
Experimental Checks
• Rotate the sample azimuthally while recording the spectra; strain-induced leakage will
follow the strain axis, whereas NA-induced leakage will not.
• Transfer the monolayer onto an atomically flat, symmetric substrate (e.g., h-BN) to restore
σₕ; the forbidden intensities should decrease dramatically.
• Reduce the objective NA or use a back-scattering confocal aperture to suppress off-axis
collection.

Problem 17 — COHP Interpretation of Magnetism in 3d

Transition-Metal Elements
The COHP (Crystal Orbital Hamilton Population) curves plot –COHP versus energy.
Negative values (red fill in the slide) represent **bonding** interactions; positive values
represent **antibonding** states. The Fermi level (Eₚ) marks which states are occupied.
Magnetism arises when **spin splitting** lowers the total energy by preferentially filling
bonding states of one spin channel and emptying antibonding states of the opposite
channel. This is captured by the Stoner criterion: I · N(Eₚ) > 1, where N(Eₚ) is the density of
d-states at Eₚ and I the exchange integral.

Element-by-Element Analysis
Sc (3d¹ hcp) – Very few d electrons; the narrow bonding block sits well below Eₚ and is
only partially filled. N(Eₚ) is too small to satisfy the Stoner criterion → **non-magnetic**.

Ti (3d² hcp) – Like Sc but with two d electrons. Bonding states still dominate below Eₚ and
the bandwidth is large, giving a low N(Eₚ) → **non-magnetic**.

V (3d³ bcc) – Eₚ cuts through the tail of the bonding peak but N(Eₚ) remains moderate;
Stoner product ≈ 0.7. V therefore stays **paramagnetic** in the elemental phase.

Cr (3d⁵ bcc) – Half-filled d shell. Bonding and antibonding lobes are symmetric about Eₚ, so
spin polarisation gains little energy. Instead Cr adopts a spin-density-wave
(antiferromagnetic) order at low T; overall moment ≈ 0.

Mn (3d⁵ bo α) – Broader d band than Cr; some antibonding states are occupied already.
Exchange splitting is insufficient to remove these states, so bulk α-Mn remains **complex
non-collinear/weakly magnetic** rather than ferromagnetic.

Fe (3d⁶ bcc) – Large N(Eₚ) because Eₚ lies on a sharp peak at the bonding–antibonding
crossover. Spin splitting empties minority antibonding states and fills majority bonding
states, gaining ≈ 0.6 eV/atom → **strong ferromagnetism (2.2 μ_B)**.

Co (3d⁷ hcp) – Similar mechanism; slightly fuller band than Fe but still antibonding
minority states at Eₚ. Exchange splitting lowers energy → **ferromagnetic (1.7 μ_B)**.
Ni (3d⁸ fcc) – Eₚ touches the tail of antibonding states; spin splitting reduces that
occupancy, though the gain is smaller than Fe/Co → **weak ferromagnetism (0.6 μ_B)**.

Cu (3d¹⁰ fcc) – d band is completely filled (bonding and antibonding below Eₚ). N(Eₚ)
comes only from broad 4s band, so the Stoner criterion fails → **diamagnetic**.

Why COHP Explains the Trend

• Elements where Eₚ intersects **bonding tails** with low N(Eₚ) (Sc-V) cannot gain enough
exchange energy → non-magnetic.
• Where Eₚ cuts through the **bonding-to-antibonding crossover** and N(Eₚ) is high
(Fe-Ni), spin polarisation removes electrons from antibonding states, lowering total energy
→ ferromagnetism.
• A half-filled symmetric band (Cr) or a fully filled band (Cu) leaves no energetic advantage
for ferromagnetism.

Solution 18

1 Klaus von Klitzing is a German 11 Alexei A. Abrikosov was a Russian-

physicist American physicist

2 Konstantin Novoselov 12 Brian D. Josephson is a British

physicist

3 Andre Geim, 13 John Bardeen

4 Robert B. Laughlin is an American 14 Leon Neil Cooper

physicist

5 Horst L. Stormer : a German- 15 John Robert Schrieffe

American physicist

6 Daniel C Tsui : is a ChineseAmerican 16 Karl Alex Mulle physicist r was a

physicist swiss

7 Friedrich Onnes: was a Dutch 17 Geo physicist rg Bednorz was a

physicist swiss

8 Walther Meissner : was German 18 Fritz Wolfgang London and Heinz

physicist London

9 Anthony J. Leggett was a 19 Zhong physicist xian Zhao is a

BritishAmerican physicist Chinese

10 Vitaly L. Ginzburg was a Russian

physicist
(1) Klaus von Klitzing is a German physicist known for discovering the integer quantum
Hall effect in 1980, leading to the quantization of the Hall resistance in two-dimensional
electron systems, which established a precise measurement standard for electrical
resistance.

(2 -3) Konstantin Novoselov and Andre Geim, both Russian-born physicists, were
awarded the Nobel Prize in Physics in 2010 for their groundbreaking experiments on
graphene, a single layer of carbon atoms arranged in a two-dimensional honeycomb
lattice. Their work demonstrated graphene’s remarkable properties, including its
exceptional strength, electrical conductivity, and potential applications in various fields
such as electronics, materials science, and nanotechnology

(4-6) Robert B. Laughlin, Horst L. Stormer, and Daniel C. Tsui are all renowned
physicists who were awarded the Nobel Prize in Physics in 1998 for their discovery of a
new form of quantum fluid with fractionally charged excitations. Together, Laughlin,
Stormer, and Tsui’s work on the fractional quantum Hall effect opened up new avenues
of research in condensed matter physics and quantum electronics, leading to further
exploration of exotic quantum phenomena and potential applications in areas such as
quantum computing and materials science.

(7) Friedrich Onnes: Discovered superconductivity in 1911, earning his father, Heike
Kamerlingh Onnes, the Nobel Prize in Physics in 1913 for this achievement

(8) Walther Meissner is renowned for the Meissner effect, which explains the expulsion
of magnetic fields from superconductors

(9-11) Alexei A. Abrikosov, Vitaly L. Ginzburg, and Anthony J. Leggett were awarded
the Nobel Prize in Physics in 2003 for their pioneering work in the theory of
superconductors and superfluids. Their contributions have greatly advanced our
understanding of these unique quantum states of matter and have had a profound impact
on the field of condensed matter physics

(12) Brian D. Josephson is a British physicist known for his pioneering work on the
Josephson effect, which revolutionized the field of superconductivity. His theoretical
predictions led to the development of new technologies and advancements in quantum
electronics such as the development of sensitive magnetometers, superconducting
quantum interference devices (SQUIDs), and superconducting digital electronics

(13-15) They all are American phyicst. John Bardeen, Leon Neil Cooper, and John
Robert Schrieffer, collectively known as BCS, received the Nobel Prize in Physics in
1972 for their groundbreaking theory of superconductivity, which is now known as the
BCS theory. Their work provided a comprehensive explanation for the phenomenon of
superconductivity, outlining how electrons in a superconductor can form pairs and move
without resistance at low temperatures, revolutionizing our understanding of condensed
matter physics and leading to numerous practical applications

(16-17) Georg Bednorz and Karl Müller, both Swiss physicists, were awarded the Nobel
Prize in Physics in 1987 for their discovery of high-temperature superconductivity in
ceramic materials, opening new avenues for research and practical applications in the
field of condensed matter physics. Their groundbreaking work paved the way for
advancements in superconducting technology and has significant implications for various
industries.

(18) The London brothers, Fritz and Heinz London, were German-born American
physicists renowned for their pioneering work in the field of superfluidity and
superconductivity. Their groundbreaking theoretical insights, particularly the
development of the London equations, laid the foundation for our understanding of the
macroscopic quantum behavior of superfluids and superconductor

(19) Zhongzian Zhao has contributed significantly to the understanding of high-

temperature superconductivity through his theoretical frameworks, notably proposing
models that explain the mechanisms behind these phenomena.

Problem 19 ― Applying the Euler Characteristic in Carbon Polyhedra

1 Verify χ for Standard Polyhedra (g = 0)

Tetrahedron: V = 4, E = 6, F = 4 ⇒ χ = V – E + F = 2 = 2 ✓

Hexahedron (Cube): V = 8, E = 12, F = 6 ⇒ χ = V – E + F = 2 = 2 ✓

Octahedron: V = 6, E = 12, F = 8 ⇒ χ = V – E + F = 2 = 2 ✓

2 Counting Pentagons in the Fullerene C₆₀

Let P = number of pentagons, H = number of hexagons (faces). Every carbon atom is
3-coordinated, so:

• Vertex count: 3V = 5P + 6H ⇒ V = (5P + 6H)/3

• Edge count: Each edge belongs to 2 faces ⇒ E = (5P + 6H)/2

• Face count: F = P + H

Insert these into Euler’s relation V – E + F = 2 (sphere, g = 0):

(5P+6H)/3 – (5P+6H)/2 + (P+H) = 2

 Multiplying by 6 gives P = 12 (independent of H).

For C₆₀ we have V = 60. Using 5P + 6H = 3V gives 5·12 + 6H = 180 ⇒ H = 20.

⇒ **C₆₀ contains exactly 12 pentagons and 20 hexagons.**

3 Pentagons Required to Cap a Carbon Nanotube

A perfect nanotube wall is a rolled graphene sheet (all hexagons, χ = 0). Closing one end
into a hemispherical cap restores genus 0 and demands positive Gaussian curvature
supplied by pentagons. Half of the 12 pentagons of a full fullerene are needed per cap:

• **6 pentagons per end-cap**

• Thus a nanotube capped at both ends contains **12 pentagons in total** (distributed
6 + 6).