Spectroscopy Lecture Note 1
Spectroscopy Lecture Note 1
DEPARTMENT OF CHEMISTRY
CH 2012
(45L, 3C)
First Semester, February 2020
Spectroscopy (12 L)
By
Topics to be discussed
Introduction
Physical basis of spectroscopy 5 Lectures
Electronic Spectroscopy (UV/Vis)
VibrationSpectroscopy (IR)
• Rotational Spectroscopy (Microwave) 5 Lectures
• Vibration-Rotation Spectroscopy
NMR Spectroscopy (NMR, Radiowave)
Mass Spectroscopy (MS) 2 Lectures
2
Learning Outcomes:
3
The dictionary definition of spectroscopy:
•What is Radiation?
•What is Matter?
•Interaction of radiation and matter, How?
Definitions, theories, etc…
4
Electromagnetic (EM) radiation
5
Electromagnetic Spectrum
7
Measurable variables
• Wavelength () is the distance between any two
identical points in consecutive cycles
• Frequency () is the number of cycles the wave
undergoes per second.
is found in units of: mm (micro, 10-6)
nm (nano, 10-9)
pm (pico, 10-12)
Angstroms (Å, 10-10)
is found in units of s-1 (1/s) or Hertz (Hz)
8
Wavelength, Frequency & Energy
9
So which has the highest energy…
ultraviolet, visible or microwave?
10
Wave Theory
=c
Where c is the speed of radiation (light) 2.998 108 ms-1
1
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Atomic and Molecular Energy Levels
Principal N 1,2,3,…
Azimuthal L 0,…N-1
Magnetic ml l….0…-l
Electron spin ms +1/2, -1/2
Vibrational V 0,1,…
Rotational J 0,1,…
Nuclear spin I n/2 (n = 1,2,…)
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Because the energy levels associated with a molecule are discrete
transition b/w the various energy states will only occur at certain
discrete energies.
h
E
h
Absorption Emission
(1)
(2) (3)
(1) Electronic transition (γ rays to UV/Vis region)
(2) Vibrational transition (Infra Red region)
(3) Rotational transition (Microwave region)
Because these particles, atoms and molecules have very different masses, transitions
occur at very different energies and according to the Born-Oppenheimer
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approximation they can be considered as separate.
E = Eelec. + Evib. + Erot. + Etrans. (Energy is partitioned)
Wavelength Energy Range (Jmol-1) Time Spectroscopic Process Occurring
Range (m) Scales (s-1) Technique
(2-9) × 10-7 (1-6) × 105 10-14 UV-Visible Change in Elec.State
Spectroscopy is the study of the way in which electro magnetic radiation interacts with
matter as a function of frequency (or wavelength).
Detector
Light source Absorption Cell 18
• The beam from tuneable source (e.g. lasers) of radiation is passed
through the sample in a cell.
• Intensity is measured by the detector.
• Variation of the signal intensity as the frequency of the radiation is
scanned is called the spectrum.
Consider a molecule
•Because there is more than one significantly populated lower energy states, or
because it is possible for excitation in more than one state to occur.
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Fine Structure
Ab Ab
Ab Ab
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Population Distribution
• Need to know which levels are significantly occupied and hence likely to
undergo absorption of energy.
• If upper and lower energy levels are equally populated then absorption
and emission are both equally likely and so no spectroscopic transition
will be seen.
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Spectroscopic transitions only occur when there is a difference in
populations.
There is another important factor for a transition to occur. This arises from the use of
quantum theory, which imposes certain limitations on which transitions should occur.
The rules that govern which of these transitions have a finite (i.e. non-zero) probability
of occurring are called selection rules.
Electronic Spectroscopy
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Vibrational Spectroscopy
Rotational Spectroscopy
NMR Spectroscopy
Δm = ±1 m = I, I-1, I-2….,0,….,-I+1, -I
I – Spin quantum number of the nucleus
Nucleus will possesses a magnetic moment when I≠0
(2I + 1) possible orientations from which transitions resulting in a change of Δm = ±241 are
allowed.
Time Scales
Relaxation time (τ) is the time required to revert to the ground state. τ
varies from technique to technique.
I0 I
Energy
Energy Energy
Analyser
Source Selector
ref. beam
Computer Output
Light Path 26
------- Electrical Connections
Final spectrum will usually be a plot of Absorbance (A) or how much energy has been
absorbed, versus energy. Alternatively the proportion of energy that has passed through
the sample, the Percentage transmission (%T) can be plotted against energy.
A %T
Energy Energy
I
A log 10 0 T I 100
I I0
•If 20% absorbs, 80% will pass through
•If second identical sample is additionally placed in the sample beam then a further
20% of the remaining energy i.e. 16% (20% of 80%) would be absorbed and 64%
(100-20-16) will be transmitted.
•Doubling the sample result in less than a doubling of the absorbed peak in the %T
scale. However doubling of the absorption can be seen. 27
A1 log10 100 0.097 A 2 log10 100 0.194
80 64
For this reason most spectroscopic techniques present the ordinate axis of spectra in terms of
absorption, rather than transmission, the common exception being IR spectroscopy.
x x + dx
I + dI I
log10(I0/I) is known as Optical Density (OD) or Absorbance (A) which is proportional to the
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concentration.
Atomic Absorption Spectroscopy (AAS)
Flame (high T)
2P
I
1/2 I0 (HCL)
590 nm
2S
1/2 NaCl
•Qualitative studies
•Quantitative studies Calibration curve
A cl
A
Atomic Emission
c
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Electronic (UV/VIS) Spectroscopy of Molecules
The UV/VIS spectra of molecules (e.g. organic) are associated with transition b/w
elec. energy levels. The transitions are generally b/w a
•Bonding or lone pair orbital and
•An unfilled non-bonding or anti-bonding orbital.
Higher energy separation is found when electrons in σ bonds are excited (120 – 200
nm). This range is known as the vacuum ultra violet (vacuum UV).
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A or ε
Spectrum A or ε
λmax λ
Due to interactions of solute with the solvent molecules, the vibration and rotation fine
structure is usually blurred out and a smooth curve is observed.
Choice of solvent: 95% ethanol transparent down to about 210 nm and 1cm cells are used.
Selection rules (Have already done)
ε = 0.87 × 1020 × P × a
The spectra of chromophores with εmax less than about 10,000 are the result of
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forbidden transitions.
Chromophores
The word chromophore is used to describe the system containing the electrons responsible for
the absorption in question.
** Forbidden transition of ketones – one of the lone pair electrons (n) on the O atom
to the lowest anti-bonding orbital (π*) of the carbonyl group.
The longer the conjugated system, the longer the wavelength of the
absorption maximum.
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Solvent Effects
π π*
(CH3)2C==O : n π*
+
H2N NH3
H+
230 nm 203 nm
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Consider a simple harmonic motion of a mass m hanging from a spring.
Simple harmonic motion
l
d2 x 2 1 k
ω x 2 m
x dt 2
mg
Consider a diatomic molecule
re
x1 x2
k m1m2
1
2 m1 m2
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Normal Vibration Modes
The description of the 3N –6 (or 3N –5) molecular vibrations is greatly
simplified when normal modes of vibrations are considered. A normal
mode of vibration is one where each nucleus executes simple harmonic
oscillations about its equilibrium position. All the nuclei move with the
same frequency and are in-phase and the center of mass of the molecule
remains unaltered.
Example: CO2 modes of vibration
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How many normal modes of vibration are there for the following
molecules: H2O, H2O2, C2H4 , H C C C CH?
N vib 3N 6 or N vib 3N 5
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Normal Vibration Modes
Each normal mode of vibration is treated
as the simple harmonic oscillation of
what is termed a normal coordinate. The
normal coordinate is constructed so that
it expresses all the individual
displacement of the nuclei involved.
In the following, only linear diatomic
molecules will be considered. The
(unique) normal coordinate corresponds
in this simple case to the internuclear
distance.
Normal coordinate
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k 1 k
1 Hz
2c
cm1
2
Vibrational energies, like all other energies, are quantized, and and the
allowed vibrational energies for any particular system may be calculated
from the Schrödinger equation. For the simple harmonic oscillator these
turn out to be:
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Ev 1 cm1
v v
hc 2
46
Applying the selection rule
11/2
v 1v (v 1 1 2 ) v 1 2 cm 1
3/2
1/2
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The harmonic oscillator is an acceptable approximation only for small
deviation from the equilibrium internuclear distance (vibrations of small
amplitude).
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V(r)
r
re
V(r) = (1/2)k(r – re)2
V(r)
D0 De
r
V(r) = De [1 – e-a(r - re)]2
De = D0 + ½(h) 49
When the Morse anharmonic potential is used, the permitted vibration
energy levels are defined by the expression:
1 1 2 ~ cm 1
E v (v ) x e (v ) e
2 2
v 0,1, 2,..., v m ax
Xe – anharmonocity constant
Do
De
1 1 2 ~
E v hc (v ) x e (v ) e
2 2
D0 De
E0
Do
D e 5.33eV h 6.6260810 34
Js 1
De
~ 2989.7 c m 1
e c 2.997910 8 ms 1
x e~e 52.05 c m 1 1eV 1.60217710 1 9 J
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