CYN-525

Advanced Molecular
Spectroscopy
Lecture 6

Dr. Pavan Kumar

Relaxation mechanisms
Dipolar mechanism
Dipole-dipole interaction
Effective over short distances (<5Å ;
1/𝑟 3)
Gyromagnetic ratio of the nuclei
creating the local field and the nuclei
experiencing it
orientation of the vector joining the
two nuclei to the applied field
reorientation possible via a single
close nuclei or large number of
remote nuclei
Chemical anisotropy Paramagnetic species
Induced local diamagnetic field due to Electron have a much higher gyromagnetic
electron cloud (chemical shift) ratio and hence stronger influence
Magnitude of induced field (Bloc) Even low concentrations of unpaired
depends on the orientation of molecule electron species
in the applied field (anisotropic)
‘Degassing’ of NMR sample
Bloc can have any direction (enables
relaxation)
Most nuclei have chemical shift
anisotropy
Proton-decoupled spectra

Removes the interactions between the 1H and 13C

Removes multiplets and simplifies the spectrum

Irradiate all the protons with a broad spectrum of frequencies

in the proper range – second tunable RF generator
(decoupler)

Saturation of spins states of protons

Decouple any spin-spin interactions between 1H and 13C.

13C only ‘senses’ an average spin of the 1H

13C with attached hydrogens have higher intensities

Nuclear Overhauser Enhancement (NOE)

More hydrogen atoms attached to the carbon the higher the enhancement

NOE shows up when one of the two different type of atoms is irradiated while the
NMR spectra of the other is being recorded

Effect can be positive or negative depending on the types of atoms involved Albert Overhauser

1 𝛾𝑖𝑟𝑟
𝑁𝑂𝐸𝑚𝑎𝑥 =
2 𝛾𝑜𝑏𝑠

𝛾𝑖𝑟𝑟 - irradiated nucleus

𝛾𝑜𝑏𝑠 - observed nucleus

𝑇𝑜𝑡𝑎𝑙 𝑝𝑟𝑒𝑑𝑖𝑐𝑡𝑒𝑑 𝑖𝑛𝑡𝑒𝑛𝑠𝑖𝑡𝑦 (maximum) = 1 + NOEmax

1 267.5
𝑁𝑂𝐸𝑚𝑎𝑥 = = 1.988 200% enhancement (theoretical maximum)
2 67.3
 Original Overhauser Effect
Nuclear spin with electron spin
Enhancement observed in nuclear spin

W – probability of relaxation transitions (maintenance of boltzman distribution

W1 & W1’ correspond to probability for longitudinal

Albert Overhauser relaxation of nuclear and electronic spins
W2 & W0 correspond to transition probabilities
where both spins flip simultaenously
Population Probability

At equilibrium

Boltzmann law

Population differences are defined by a

larger energy gap
 Nuclear Overhauser Effect
Solomon equation
Z-magnetization of nucleus X
Equilibrium magnetization

For a homonuclear case 𝛾𝐴 = 𝛾𝑋 signal enhancement of 50%

Negative NOE – negative gyromagnetic ratio – 15N or 29Si

NOE will be less if relaxation is occurring via other pathways

than dipolar mechanisms
NOE: Origin

Cross-polarization : polarization of spin states in one type of nucleus causes a polarization of the spin states in another nucleus

For eg: In case of 1H and 13C – when the 1H are saturated – there are more spins in the excited state than normal which causes
Carbon nuclei spins to establish a new equilibrium with more spins in the lower state.

This increase of population in the lower spin state of carbon increases the intensity of the NMR signal

Single-quantum transitions (only one spin at a time)

N3 and N2 – similar energies - populations

NOE: Origin
W2 greater than W0 positive NOE

Intensities in NMR are W0 greater than W2

proportional to difference in negative NOE
populations

N4 = N2; N1 = N3 Irradiate protons W0

Double-quantum transitions (relaxation) (W2)

NOE: Uses

NOE effect is very useful for 13C NMR to counteract the isotope abundance issue

NOE effect operates both ways – either atom can be irradiated and if the 13C were irradiated – there is a minimal
enhancement of 1H spectra – due to isotope abundance and the 𝑔𝑦𝑟𝑜𝑚𝑎𝑔𝑛𝑒𝑡𝑖𝑐 𝑟𝑎𝑡𝑖𝑜

NOE effect of the Hydrogens can extend to carbons beyond what they are connected to and is a through space coupling

1 Molecular ruler
𝑁𝑂𝐸 = 𝑓 3
𝑟

NOE- enhanced proton-coupled spectrum

Chemical Exchange
Gives insight into the secular contribution of T2 relaxation

The frequency separation between the

Rate of the exchange process </>
resonances in the two environments

Fast exchange

Exchange narrowing
Exchange broadening Assumption : Populations of A
and B are same. kf = kb = kex

Slow exchange
 Chemical Exchange

1000 spins FID simulation

Different precession frequencies due to different chemical environments

Chemical Exchange

In short time periods – difficult to resolve signals with close frequencies

Phase difference = 2𝜋Δ × 𝜏

𝜏 − time; ∆ − frequency difference

1
10.5 Hz For the phase difference to be significant - 𝜏 ≈
∆
10 Hz 1
For a chemical exchange process (first order) 𝜏𝑒𝑥 =
𝑘𝑒𝑥
2𝜋Δ
𝑘𝑒𝑥 ≫ ∆𝐴𝐵 Fast exchange Phase difference =
𝑘𝑒𝑥

𝑘𝑒𝑥 ≪ ∆𝐴𝐵 Slow exchange