Nuclear magnetic resonance

Nuclear magnetic resonance

The use of NMR in chemical research was

pioneered by Herbert S. Gutowski of
Department of Chemistry, University of
Illinois, who established the relationship
between chemical shifts and molecular
structures. He also discovered spin-spin
coupling.
Foundation of magnetic spectroscopy.
Proton NMR.
Circular electric current =
magnet

Electrons in p, d, f orbitals
Electron spin
Nuclear spin

charge

q
magnetic
moment
m= l angular
momentum
2m

mass
 Magnet-magnetic-field
interaction
Classical
high energy

DE = - m × B

Quantum

Ĥ1 = - m̂ × B
q ˆ
=- l ×B
low energy
2m
qB ˆ
=- lz
2m
Tesla
C T (Tesla)

qB
J
DE = - lz kgm2/s

2m
kg

1 T = 1 V s / m2 Nikola Tesla
Public domain image from Wikipedia

Field strength in 500 MHz NMR ($0.5M) = 11.7 T

Field strength in 1 GHz NMR ($20M) = 23.5 T
Strongest continuous magnetic field = 45 T
(National High Magnetic Field Lab at Tallahassee, FL)
Electrons in p, d, f orbitals
First-order perturbation theory

qB ˆ qB (0) ˆ (0) qB
Ĥ 1 = - lz DE = - Y 0 lz Y 0 = - ml
2m 2m 2m
e
= ml B = mB ml B
Bohr magneton
9.724×10−24 J/T
2me
ml = +2 ; DE = +2 mB B
(2 l + 1)-fold ml = +1 ; DE = +1mB B
degeneracy ml = 0 ; DE = 0 mB B
(field off)
ml = -1 ; DE = -1mB B
ml = -2 ; DE = -2 mB B
Zeeman effect (field on)
Electron spin
Quantum electrodynamics

DEorbit = mBml B DEe-spin = ge mBms B

g-value
2.002319…

α 1 1
ms = + ; DE = + ge mB B
2-fold 2 2
degeneracy ge mB B
(field off)
1 1
ms = - ; DE = - ge mB B
2 2
β
ESR or EPR (field on)
Nuclear spin Nuclear magneton e
1800 times smaller
than Bohr magneton
2mp
Proton
DEe-spin = ge mBms B DEn-spin = - gI mN ms B mass

Negative sign Nuclear g-factor

positive nuclear charge proton: 5.586

β 1 1
ms = - ; DE = + gI mN B
2-fold 2 2
degeneracy gI mN B
(field off)
1 1
ms = + ; DE = - gI mN B
α 2 2
NMR (field on)
Proton NMR
Sweep coils

gI mN B

α
Radio freq Sample
Proton NMR spectra
(1) Overall intensity
(2) Groups of peaks
(3) Relative intensities of groups of peaks
(4) Pattern in each group (hyperfine structure)
Overall intensity
β
N b = Na exp ( -DE / kBT ) » Na (1- DE / kBT )

DE = gI mN B excess
α spins
Na
α
Intensity of a NMR signal
~ energy of RF radiation absorbed / time
~ ΔE × number of excess α spins
~ B2 / T

Stronger magnet + lower temperature

Group of peaks:
chemical shifts
Resonance freq. Resonance freq. of TMS
Si(CH3)4
n -n
Chemical shift
d= ´10 6

n “ppm”

DE = gI mN B

α
Group of peaks:
chemical shifts
Resonance freq.
Shielding
n -n constant
Chemical shift
d= ´10 6

n
hn = gI mN Blocal = gI mN (1- s ) B
Blocal
B
Group of peaks: chemical
shifts
Shielding
constant
hn = gI mN Blocal = gI mN (1- s ) B

Blocal
B
+
Group of peaks:
chemical shifts Shielding
constant
hn = gI mN Blocal = gI mN (1- s ) B
Group of peaks: chemical
shifts
n -n
d= ´10 6
n
RCH3
-CH2-
-CH-
ROH
ArOH
Ar-H
-CHO
-COOH
14 12 10 8 6 4 2 0 δ
Relative intensities
C2H6O
RCH3

H H2 -CH2-
OH CH2 H3 ROH
CH3
4 2 0
δ

CH3CH2OH
Hyperfine structure Spin-spin coupling: hJms ms¢
H nearby H
1
CH3CH2OH β - hJ
4
β

α
1 1
OH CH2 CH3 gI mN B gI mN B - hJ gI mN B + hJ
2 2
α
β
α
Hyperfine structure
Spin-spin coupling: hJms ms¢
H H H2
ββ
CH3CH2OH β β
βα, αβ
α
αα
OH CH2 CH3 gI mN B
αα
α
αβ, βα
β
α ββ
Hyperfine structure
Pascal’s triangle

CH3CH2OH 1

nearby H 1 1
OH CH2 CH3
nearby H2 1 2 1

nearby H3 1 3 3 1

nearby H4 1 4 6 4 1
Hyperfine structure

CH3CH2OH Q: Why doesn’t the proton in the OH group cause

splitting?
A: The proton undergoes a rapid exchange with
protons in other ethanol or water molecules; its
OH CH2 CH3
spin is indeterminate in the time scale of
spectroscopic transitions; this causes lifetime
broadening of spectral line rather than splitting.
?
Hyperfine structure

CH3CH2OH Q: Why is there no spin-spin coupling between the

two protons in the CH2 group?
A: There is spin-spin coupling between them;
however, its effect on the peaks is null and
OH CH2 CH3
undetectable; this is because these protons are
chemically and magnetically equivalent.
? ?
Hyperfine structure
ì a (1) a ( 2 ) MS = 1
Triplet ïï
magnetic í a (1) b ( 2 ) + b (1) a ( 2 ) MS = 0 S =1
CH3CH2OH ï
ïî b (1) b ( 2 ) M S = -1

a (1) b ( 2 ) - b (1)a ( 2 ) M S = 0 S=0

Singlet
non-magnetic

DEspin-orbit = 12 hcA { j ( j +1) - l ( l +1) - s ( s +1)}

DEspin-spin = 12 hJ {S ( S +1) - s ( s +1) - s¢ ( s¢ +1)} = 12 hJ {S ( S +1) - 23 }
+ 14 hJ
M S = -1
+ 14 hJ No change in spacing
MS = 0
+ 14 hJ
MS = 1
no spin-spin coupling with spin-spin coupling
Spin-spin coupling
constant

1
J HH H H

2
J HH H C H

3
J HH H C C H
Spin-spin coupling
constant
H H
DE = hJ ( 12 ) ( - 12 ) < 0
J HH > 0
Fermi Fermi 1
contact contact
Covalent bond
singlet-coupling

higher energy??

Fermi contact
lower energy!
Spin-spin coupling
constant

DE = hJ ( 12 ) ( 12 ) < 0
H C H

Fermi
contact
Hund Fermi
contact
2
J HH < 0
Covalent Covalent
bond bond
singlet singlet
coupling coupling
Spin-spin coupling
constant

H C C H
H
j
C H
Karplus equation

3
J HH = A + Bcosj + C cos2j
Martin Karplus
Department of Chemistry
University of Illinois Image (c) University of Illinois
ILLIAC
Magnetic resonance
imaging: MRI

Resonance frequency
~ location (x)

Intensity
Public domain image from Wikipedia
~ number of protons (in water) at x
Paul Lauterbur (far right)
Department of Chemistry
University of Illinois
Summary
We have studied the foundation of magnetic interactions and magnetic
spectroscopy.
We have learned the theory of proton NMR as an essential tool for chemical
structural analysis.
The origins of chemical shifts, hyperfine structures, and spin-spin coupling
constants are discussed as well as their relation to molecular structures.