CYN-525

Advanced Molecular
Spectroscopy
Lecture 2

Dr. Pavan Kumar

Fatayer et al., Science 365, 142–145 (2019)
Nuclear Spin

• Spin is a quantum mechanical concept - there is no classical analogy

• Every nucleus with a net spin - the spin quantum number determines the number of spin states allowed

• Spin Quantum Number (I) – The number of allowed states is 2I+1 ranging from +I to –I
+I, I-1….. (-I+1), -I

For a proton, For a chlorine nucleus ( 35

17𝐶𝑙),
𝟏 𝟏 𝟑 𝟏 𝟏 𝟑
+ ,− + ,+ ,− ,−
𝟐 𝟐 𝟐 𝟐 𝟐 𝟐
Nuclear Spin

Commonly studied nuclei in Chemistry and Biology

Proton (1H), Deuterium (2H), Carbon (13C), Nitrogen (15N), Phosphorous (31P)

Spin ½ nuclei are relatively easy to study

11B, 10B, 27Al, 17O, 29Si, etc. are studied in inorganic chemistry and materials science
Nuclear Magnetic Moment

Charged nucleus (1H) rotating with angular velocity creates a magnetic field of its own

Nucleus with spin will have a magnetic moment, µ

A 1H nucleus may have a clockwise (+1/2) or counter-clockwise (-1/2) spin – magnetic moment in opposite directions

In the absence of magnetic field, all spin states are degnerate

Interaction with Magnetic Field
When a magnetic field is applied, the magnetic moments of nuclei align either in the direction of the field or opposite to it
For a nuclei with two spin states,

removal of degeneracy
Stern-Gerlach Experiment
Rabi Experiment
NMR Absorption

Energy absorption is quantized and should equal the difference in energy between the two states

Δ𝐸 ∝ 𝐵0 (magnetic field)

Δ𝐸 ∝ 𝛾 (𝑚𝑎𝑔𝑛𝑒𝑡𝑜𝑔𝑦𝑟𝑖𝑐 𝑟𝑎𝑡𝑖𝑜)
ℎ
Δ𝐸 = 𝛾 𝐵 = ℎ𝜈
2𝜋 0
𝛾
𝜈= 𝐵
2𝜋 0

For an unshielded proton,

𝛾 = 26.75; 𝜈 = 42.6 𝑀𝐻𝑧; 𝐵 = 1 𝑇𝑒𝑠𝑙𝑎
Magnetogyric ratio

𝑞 • ratio of magnetic moment to angular momentum

𝛾=
2𝑚 • Constant for a nucleus
q is charge; m is mass • experimentally determined

Side note: NMR , ESR

Classical Picture (Resonance)

Spinning top
Precesses in the presence of
gravitational field

Spinning nucleus Precession of the nucleus generates an oscillating

Precesses in the presence of
magnetic field
The angular frequency of prescession
about its own axis of spin – Larmor
Frequency
Larmor frequency is proportional to
the strength of the magnetic field
applied.
electric field of the same frequency.
When frequency of the incoming radiation matches
the frequency of the electric field generated by the
nucleus – energy is absorbed causing a spin change
This condition is called resonance

𝜔 = 60 𝑀𝐻𝑧; 𝐵 = 1.41 𝑇𝑒𝑠𝑙𝑎

Quantum mechanical picture
𝜈 = 60 𝑀𝐻𝑧; 𝐵 = 1.41 𝑇𝑒𝑠𝑙𝑎
∆𝐸 = ℎ𝜈 = 2.39 × 10−5 𝑘𝐽/𝑚𝑜𝑙𝑒
Thermal energy at RT is enough to populate both the energy levels

There will be a slight bias in the population densities due to the small energy difference – Boltzmann Distribution

𝑁𝑢𝑝𝑝𝑒𝑟
= 𝑒 −∆𝐸Τ𝑘𝑇 = 𝑒 −ℎ𝜈Τ𝑘𝑇
𝑁𝑙𝑜𝑤𝑒𝑟

Solve for this at 298 K when 𝜈 = 60 𝑀𝐻𝑧

𝑁𝑢𝑝𝑝𝑒𝑟 1000000
= 0.999991 =
𝑁𝑙𝑜𝑤𝑒𝑟 1000009

In 2 million nuclei, the lower level has an excess of only 9 nuclei – Excess population (responsible for NMR signal)

When the excess population is zero – saturation The RF signal if too strong can lead to saturation
Sensitivity of NMR
Increase in sensitivity with increase in Magnetic field strength

Increasing B0
Gyromagnetic ratio increase - sensitivity increases

Decrease in sensitivity with increase in Temperature

Chemical Shift
Tetramethylsilane – reference compound
Electron density around the nuclei differentiates them (the H are more shielded here than
most other compounds)

Across different instruments with different

magnetic field strengths – different shifts in
frequency.

Local diamagnetic current

Chemical shift (𝛿)
𝑠ℎ𝑖𝑓𝑡 𝑖𝑛 𝐻𝑧
𝛿=
Diamagnetic shielding or 𝑠𝑝𝑒𝑐𝑡𝑟𝑜𝑚𝑒𝑡𝑒𝑟 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦 𝑖𝑛 𝑀𝐻𝑧
Diamagnetic anisotropy

162 𝐻𝑧 270 𝐻𝑧
𝛿= = = 2.70 𝑝𝑝𝑚
60 𝑀𝐻𝑧 100 𝑀𝐻𝑧
Precession at lower frequency
(very small changes in frequency) ppm – parts per million

1H in TMS are at 0.00 ppm (by definition)

relative measurement