Spectroscopy
Motivation
Spectroscopy is the study of the interaction between matter and radiation. If the radiant energy matches the
energy of a specific excitation (electronic, rotational, vibrational, nuclear), absorption occurs. Spectroscopy
allows for the detection, identification and analysis of atoms/molecules. We will briefly discuss three types
of spectroscopy and their uses.
The electromagnetic spectrum
Radiations can be described as electromagnetic waves. The frequency, ν of a wave is the number of wave
cycles per second. It is measured in Hz, where 1 Hz = 1 s−1 . The wavelength, λ, is the length of a
complete wave cycle. It is often measured in nm. Frequency and wavelength are connected by the equation
c
ν= (1)
λ
where c is the speed of light. They are both related to the energy by the following equation
hc
E = hν = (2)
λ
where h = 6.6 · 10−34 J s is the Planck constant.
Another often used quantity in spectroscopy is the wavenumber. It is equal to the inverse of the wave
length and is expressed in cm.
1
ν̄ = (3)
λ
Figure 0.1: The electromagnetic spectrum.
IR spectroscopy
Infrared radiation is absorbed by molecules and converted into energy of molecular vibration. In IR spec-
troscopy we expose a molecule to IR radiation. If the energy of a vibrational transition matches the radiant
energy, absorption occurs.
1
IR spectroscopy
The match between the radiant energy and the transition is not sufficient to make a vibration IR active.
The vibration must involve a variation in the dipole moment of the molecule to be IR active.
Both the complexity and the wavenumbers of the peaks in the spectra give information about the molecules.
In the next figures, the main location for the most common organic functional group is detailed.
Figure 0.2: Main frequency of adsorption for the most common organic functional groups.
Peaks in IR spectra of complex molecules can be extremely hard to attribute. It is however extremely useful
to quickly identify the presence of highly IR active bonds such as carbonyls.
2
IR spectroscopy
100.
90.
80.
70.
% Transmission
60.
50.
40.
30.
20.
10.
0.
-3500. -3000. -2500. -2000. -1500. -1000. -500.
Wavenumber cm
-1
100.
90.
80.
70.
% Transmission
60.
50.
40.
30.
20.
10.
0.
-3500. -3000. -2500. -2000. -1500. -1000. -500.
Wavenumber cm
-1
100.
90.
80.
70.
% Transmission
60.
50.
40.
30.
20.
10.
0.
-3500. -3000. -2500. -2000. -1500. -1000. -500.
Wavenumber cm
-1
Figure 0.3: IR spectra of formic acid, acetic acid and acetone.
3
IR spectroscopy
100.
90.
80.
70.
% Transmission 60.
50.
40.
30.
20.
10.
0.
-3500. -3000. -2500. -2000. -1500. -1000.
Wavenumber cm
-1
100.
90.
80.
70.
% Transmission
60.
50.
40.
30.
20.
10.
0.
-3500. -3000. -2500. -2000. -1500. -1000. -500.
Wavenumber cm
-1
90.
80.
70.
60.
% Transmission
50.
40.
30.
20.
10.
0.
4000. 3500. 3000. 2500. 2000. 1500. 1000.
Wavenumber cm
-1
Figure 0.4: IR spectra of acetylsalicylic acid (aspirin), phenol and ethanol.
4
IR spectroscopy
90.
80.
70.
60.
% Transmission
50.
40.
30.
20.
10.
0.
-3500. -3000. -2500. -2000. -1500. -1000.
Wavenumber cm
-1
100.
90.
80.
70.
% Transmission
60.
50.
40.
30.
20.
10.
0.
-3500. -3000. -2500. -2000. -1500. -1000. -500.
Wavenumber cm
-1
100.
90.
80.
70.
% Transmission
60.
50.
40.
30.
20.
10.
0.
-3500. -3000. -2500. -2000. -1500. -1000.
Wavenumber cm
-1
Figure 0.5: IR spectra of benzene, toluene and octane.
5
UV-Vis spectroscopy
UV-Vis spectroscopy
UV-Visible light is higher in energy than IR light. When absorbing a UV-Vis radiation a molecule/atom
gains enough energy to be able to promote an electron from an occupied orbital to an unoccupied. The
possible transitions are
• σ → σ∗
• n → σ∗
• n → π∗
• π → π∗
The first type of transition is quite rare as it require a higher quantity of energy and is usually not included
in regular UV-Vis spectra. The second transition need less energy but the number of molecules with such
transitions is small. The most common transitions belongs to the two last types.
Beer-Lambert law Spectroscopy can be used to determine an unknown concentration of a known com-
pound. When going through a solution, light will be absorbed. There is a logarithmic dependence between
the transmission T and the product of the distance l the light travels in the medium, the molar absorp-
tivity ε and the molar concentration c.
I
T = = e−εld (4)
Io
This relation is called the Beer-Lambert law. If we consider the absorbance, A = − log10 (I/Io ), we
obtain a linear relation with εld. Therefore, by knowing the sample length and the molar absorbance from
a reference sample, we can determine the concentration of a unknown sample.
Note that the molar absorbance is a function of the wavelength of the light used. If we have a solution
containing two molecules, the concentrations can also be found using the same technique. This time however,
two measurement at two different wavelength are needed and the molar absorbance of both substance must
be known for both wavelength.
5.0
4.5
% Transmission
4.0
3.5
3.0
2.5
170 180 190 200
Wavenumber cm
-1
Figure 0.6: UV-Vis spectrum of benzene.
6
NMR spectroscopy
5.0
4.5
Absorbance 4.0
3.5
3.0
2.5
240 260 280 300
Wavenumber cm
-1
3.06
3.04
3.02
Absorbance
3.00
2.98
2.96
270 280 290 300 310 320
Wavenumber cm
-1
Figure 0.7: UV-Vis spectra of acetone and pyrrole.
NMR spectroscopy
The nuclear spin quantum number I is a fixed characteristic property of a nucleus. Deriving from this spin
quantum number we can assign this nucleus the following properties
1/2
• An angular momentum of magnitude I(I + 1) ~.
• A component of angular momentum ml ~ on a specified axis (‘the z-axis’), where ml = −I, −I + 1,
. . . , I.
• If I > 0, a magnetic moment with a constant magnitude and an orientation that is determined by the
value ml .
According to the second property, the spin, and hence the magnetic moment, of the nuclei may lie in 2I + 1
different orientations relative to an axis. In absence of a magnetic field, all these orientations are degenerate,
they have the same energy. When a magnetic field is lifted, the degeneracy of the different orientations is
lifted and the spins all falls in the ground state.
The Nuclear Magnetic Resonance spectroscopy uses radiowaves in order to force transitions between the
different states ml of the nuclear spin. If a radio frequency matches a transition, absorption will occur.
7
NMR spectroscopy
The chemical shift
When recording a NMR spectrum, we focus on a single type of nucleus. This can be done as the transition
of different nuclei in the same magnetic field will occur at different energies. The energy of the transitions
will also be dependent on the magnetic field. The stronger the magnetic field, the more energy is needed to
‘flip the spin’ of a nucleus. Variation of the absorption wavelength for a single type of nucleus can therefore
be related to a change in the ‘effective’ magnetic field. The local magnetic field is defined as
Bloc = Bo + δB = (1 − σ)Bo (5)
where σ is the shielding constant. The shielding is mainly resulting from the movement of the electrons
inside the magnetic field. Therefore, nuclei in different electronic environment will have a different shielding.
The resonance frequency for a given shielding is given by
γBo
ν = (1 − σ) (6)
2π
where γ is the magnetogyric ratio of the nucleus.
The δ scale Resonance frequencies are expressed in terms of an empirical quantity called the chemical
shift δ. It is related to the difference between the resonance frequency of a standard nucleus and the one
under scrutiny.
ν − νo
δ= × 106 (7)
νo
For the case of proton the standard is the proton in TMS (tetramethylsilane, Si(CH3 )4 ), which is rich in
proton and dissolves without reactions in many liquids. Other references are used for other nuclei. The
advantage of the δ scale is that it is independent from the applied magnetic field.
(1 − σ)Bo − (1 − σ o )Bo 6 σo − σ
δ= × 10 = × 106 ≈ (σ o − σ) × 106 (8)
(1 − σ o )Bo 1 − σo
As the shielding σ decrease, the chemical shift δ increases. Therefore we speak of nuclei with high chemical
shift as deshielded and those with low chemical shift as shielded.
Origin of the shielding constant Calculation of the shielding constant is difficult. It requires detailed
information about the electron density in both the ground and the excited states as well as the excitation
energies of the molecule. Empirical approaches suggest to split the shielding constant into three components:
σ = σ(local) + σ(neighbour) + σ(solvent) (9)
The local contribution, σ(local), results of the contribution of the electrons of the atoms containing
the considered nucleus. The neighbouring group contribution, σ(neighbour), is the contribution of
the groups of atoms that form the rest of the molecule. The solvent contribution, σ(solvent), is the
contribution from the solvent molecules.
The fine structure
Resonance frequencies splits into individual lines due to spin-spin coupling between the different nuclei.
The resulting structure is called the fine structure of the spectrum. The stress of the interaction between
the nuclei is the scalar coupling constant J measured in Hz. The energy of the coupling between two
interacting spins is proportional to their scalar product E = (hJ/~2 )I1 · I2 . As the scalar product of two
vectors depend on the angle formed by the vectors, the spin-spin coupling is dependent on the relative
orientation of the spins. For nuclei constrained in a magnetic field, the only relevant contributions are in
the z-direction. E ∝ I1z I2z . The possibles values for Iz being ml ~, we obtain an energy coupling of
Em1 m2 = hJm1 m2 (10)
Energy of coupled systems
Let’s consider a system AX of spin- 21 nuclei. There are four possible spin states:
αA αX αA βX βA α X βA βX (11)
The energy of the system without spin-spin coupling is defined as
EmA mX = −γ~(1 − σA )Bo mA − γ~(1 − σX )Bo mX = −hνA mA − hνX mx (12)
8
NMR spectroscopy
where νA is the resonance frequency of the nucleus A and νX the one of atom X and mA and mX their
quantum number (mA = ± 21 , mX = ± 12 . Without spin-spin coupling, transitions βA ← αA when atom X
is in either state α or β have the same energy ∆E = hνA . The same is also true for transitions of the atom
X. If we turn on the spin-spin coupling, the energy of the system becomes
EmA mX = −hνA mA − hνX mx + hJmA mX (13)
Calculating the energy of the transition gives this time to separate energies
1
∆E = hνA ± hJ (14)
2
and
1
∆E = hνX ± hJ (15)
2
Therefore, resonance for A and X consists of a doublet of separation J centred on the chemical shift of
A/X.
Equivalent nuclei
A group of nuclei are chemically equivalent if the are related by a symmetry operation of the molecule
and have the same chemical shifts. Nuclei are magnetically equivalent if they are chemically equivalent
and have identical spin-spin coupling with any other magnetic nuclei in the molecule.
The difference between chemical and magnetic equivalence can be demonstrated using the molecules CH2 F2
and CH2 CF2 . Although in both cases, both protons are chemically equivalents, in CH2 CF2 , they are not
magnetically equivalent. One has a trans-planar coupling with one of the F atoms while the other has
a cis-planar coupling with this same atom. In the case of quickly rotating groups such as methyl, the
differences can be averaged out by the rotation.
One interesting feature of magnetically equivalent nuclei, is that although they couple together, the coupling
does not spilt the spectrum.
Coupling pattern
We have seen that in AX systems, spin-spin coupling results in a doublet of lines. Let’s now consider more
complex molecules. For a molecule AXn , the resonance of atom X will still be a doublet. As mentioned
earlier, equivalent nuclei resonate as a single nucleus, the only visible coupling will come from the atom
A with a splitting J. The overall absorption will however be n times as intense. The case of A is a bit
different. The resulting splittings is shown in the following figures. It can be understood as consecutive
coupling with the different X atoms.
Figure 0.8: Splitting pattern of the A resonance for an AXn molecule where X is a (left) half-spin nucleus and (right) integer-spin
nucleus.
Chemical shift tables
In the next tables are displayed the chemical shifts of common organic functional groups.
9
NMR spectroscopy
10
NMR spectroscopy
11