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Spectroscopy Lecture Note 1

This document provides an overview of a spectroscopy course to be taught at the University of Colombo Department of Chemistry. The course will cover 12 lectures on various topics in spectroscopy including the physical basis of spectroscopy, electronic spectroscopy, vibrational spectroscopy, rotational spectroscopy, and NMR and mass spectroscopy. Students will learn about the interaction of electromagnetic radiation with matter and how spectroscopy can be used to study atomic and molecular energy levels and transitions. They will also learn how to apply various spectroscopic techniques to problems in organic structure elucidation.
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0% found this document useful (0 votes)
159 views51 pages

Spectroscopy Lecture Note 1

This document provides an overview of a spectroscopy course to be taught at the University of Colombo Department of Chemistry. The course will cover 12 lectures on various topics in spectroscopy including the physical basis of spectroscopy, electronic spectroscopy, vibrational spectroscopy, rotational spectroscopy, and NMR and mass spectroscopy. Students will learn about the interaction of electromagnetic radiation with matter and how spectroscopy can be used to study atomic and molecular energy levels and transitions. They will also learn how to apply various spectroscopic techniques to problems in organic structure elucidation.
Copyright
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We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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UNIVERSITY OF COLOMBO

DEPARTMENT OF CHEMISTRY

CH 2012
(45L, 3C)
First Semester, February 2020

Spectroscopy (12 L)

Prepared and conducted

By

Professor K. M. Nalin de Silva


Spectroscopy
(12 lectures)

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:

• Explain the Physical basis of spectroscopy


• Understand the wave and particle nature of electromagnetic radiation
• Clearly understand the absorption and emission processes
• Understand the Laws governing absorption
• Explain the population distribution using Boltzmann distribution
• Understand the population inversion and Laser action
• Understand the Selection rules for all spectroscopic techniques
• Explain the Atomic Absorption Spectroscopy including instrumentation.
• Explain the solvent effects in UV Visible spectroscopy
• Understand the harmonic and anharmonic vibrations and related theories.
• Correlation of molecular properties to vibration spectroscopy
• Understand the importance of Rotational spectra in relation to molecular properties
• Explain the fundamentals of NMR spectroscopy and its applications in organic
structure elucidation.
• Understand the use of Mass Spectrometry and its applications.
• Use of all spectroscopic techniques for organic structure elucidation

3
The dictionary definition of spectroscopy:

It is the study of the interaction between radiation


and matter.

•What is Radiation?
•What is Matter?
•Interaction of radiation and matter, How?
Definitions, theories, etc…

4
Electromagnetic (EM) radiation

• Electromagnetic radiation refers to any form of


energy that travels in all directions from a single
source, such as light from the sun.

• Electromagnetic radiation is described as a wave


and is characterized by its wavelength (,
pronounced “lambda”), frequency (,
pronounced “new”) and amplitude.

5
Electromagnetic Spectrum

What about cell phone frequencies?


6
An Electromagnetic Wave

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

Which wave do you think has more energy?

9
So which  has the highest energy…
ultraviolet, visible or microwave?

10
Wave Theory

Wave like electromagnetic radiation may be defined in terms


of its characteristic frequency, ν or wavelength, λ.

=c
Where c is the speed of radiation (light) 2.998  108 ms-1

Wave theory accounts for many intrinsic properties:


propagation, reflection, diffraction, interference, and
polarization. 11
Particle Theory
Einstein’s work on the Photoelectric
effect demonstrated that radiation also
behaves as thought (Max Planck, 1900) it
consists of a stream of particles, or
photons (packets of energy).
Each of these photons has a fixed energy
that depends on the frequency or
wavelength of radiation.
Max Planck
Quantum Theory
 c
E  h    h    1900

Where h is the Planck’s constant 6.626  10-34 Js
 Undoubtedly this is the most important equation in spectroscopy. 12
For example, the frequency of the visible light with a
wavelength of 400 nm is

  c  = 3  108 ms-1 / 400  10-9 m = 7.5  1014 s-1

The energy of each light photon is

E = h = 6.626  10-34 Js  7.5  1014 s-1, E = 4.970  10 -19 J

When the value is multiplied by the Avegadro's constant


the energy for a mole of photon is obtained.

4.970  10 -19 J  6.022  1023 mol-1 = 293.3 kJ mol-1


13
Wave Number ( )

Number of waves that would occupy a 1 cm length

  1

E.g.  = 400 nm = 400  10-9 m = 400  10-7 cm

 = 1 / (400  10-7) cm = 25,000 cm-1

14
Atomic and Molecular Energy Levels

Molecules  Atoms  Subatomic particles


Energy levels are quantized (Quantum mechanics)

These energy levels are identified by a set of unique quantum numbers


(N, l, ml and ms)
Quantum number Symbol Values

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,…)
15
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

It is the study of the absorption or emission of energy arising from these


changes in energy states – that is the basis of all true spectroscopic
techniques. 16
Wide range of possible transitions that may be investigated. (Change
in shape of the molecule or even transitions of some of the much
smaller components such as electrons or nuclei.)

(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
17
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

(2-50) × 10-6 (2 - 60) × 103 10-13 IR Vibrations of


Molecules
(6-600) × 10-5 20 - 2000 10-11 Rotational or Rotations of
Microwave Molecules

0.6 - 5 (2 - 20) × 10-2 10-1 - 10-8 Change in Nuclear


NMR spin (I >1/2)

The Basic Spectroscopic Experiment

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.

No interaction – spectrum will be flat (transparent)

Consider a molecule

•Spectroscopic transitions will occur between molecules in a single well-defined


ground state to a single higher energy state corresponding an increase in just one
quantum number. Frequently however this is not the case.

•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.
19
Fine Structure

Electronic transitions may be accompanied by vibrations and rotations


(in molecules). When this occurs a number of peaks are observed.
Therefore we see so many absorptions referred to as fine structure in a
narrow energy range.

Ab Ab

 

Ab Ab
20
 
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.

In order to record a spectrum there has to be a difference


in population of the two states involved

21
Spectroscopic transitions only occur when there is a difference in
populations.

On the microscopic scale the ratio of the equilibrium population in


two states separated by an energy gap of ΔE is given by the
Boltzmann distribution.

Nupper/Nlower = Exp (-ΔE/kT)

k = 1.381  10-23 JK-1 T = Temperature in Kelvin


22
Selection Rules

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.

Expected transitions – allowed


Not expected transitions - forbidden

Electronic Spectroscopy

(1) Δl = ±1 (i.e. s  p, p  d, etc. ) (in atoms)

(2) ΔS = 0 (in molecules) – S is the spin multiplicity of the state (S = 2s + 1)

23
Vibrational Spectroscopy

Δv = ±1 v – Vibrational quantum number


v = 0  v = 1 is called the fundamental.
Δv = ±2, Δv = ±3 are called overtones.

Rotational Spectroscopy

ΔJ = ±1 J = Rotational quantum number

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

Time required for the interaction of a photon of energy with a molecule


to cause excitation is ≈ 10-18 s
which is much quicker than any electronic transition, molecular
rearrangement or vibration.

Excitation  higher energy state  Relaxation

Relaxation time (τ) is the time required to revert to the ground state. τ
varies from technique to technique.

If τ is short, method “sees” molecules in diff. states.


If τ if longer technique will see single average set of molecules.
25
Uncertainty Principle τ × ΔE ≤ h/2π

Instrumentation (Vibrational and Electronic Spectroscopy)


sample

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.

The Absorption Laws


Two laws indicate the extent to which the intensity of the incident beam is reduced (“attenuated”)
by light absorption.
l
I0 I

x x + dx
I + dI I

• The degree of absorption is proportional to the thickness of the


sample (Lambert’s Law).

• The degree of absorption is proportional to the concentration of the


sample (Beer’s Law). 28
 d I  d I
(1)  d x (2)  c
I I
Combining these laws with a constant of proportionality, ε, the molar extinction
coefficient, which is a function of wavelength for a given substance, and integrating

ln I 0   εcl  I  I 0eεcl


I l  I 
dI
  I   εcdx

I0 0
log10  I 0   kcl
 k
 I  2.303

ε units --- 1000 cm2mol-1


A  log10  I 0 
k – Decadic molar absorption
coefficient. A  kcl where
 I

log10(I0/I) is known as Optical Density (OD) or Absorbance (A) which is proportional to the
29
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

e.g. Flame test of Na (590 nm – D line)

c
30
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).

31
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

P – Transition probability a – Target area of absorbing system (Chromophores)


With common chromophores of the order of 10 Å long, a transition of unit
probability will have an ε value of 105.
•Fully allowed, ε = 10,000
•Low transition probabilities, ε = 1000

The spectra of chromophores with εmax less than about 10,000 are the result of
32
forbidden transitions.
Chromophores
The word chromophore is used to describe the system containing the electrons responsible for
the absorption in question.

Chromophore Transition λmax (nm)


σ bonded elec. C--C, C--H σ σ* 150
Lone pair Elec.
--O-- nσ* 185
--N nσ* 195
--S-- nσ* 195
C=O: nπ* 300 (**)
C=O: nσ* 190
π bonded elec.
C=C (isolated) π π* 190

** 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 important chromophores are those in which conjugation is present. 33


π* LUMO π*
x y
HOMO π
π

C==C C=C=C=C C==C

Isolated double bond – 190 nm (x) Ethylene


Conjugated double bond – 217 nm (y) Butadiene

The longer the conjugated system, the longer the wavelength of the
absorption maximum.

34
Solvent Effects

π  π*

• Franck Condon Principle states that during the elec. transition


atoms do not move. E’s however, including those of the solvent
molecules may re-organize.

• Most transitions, excited state is more polar than ground state.

• Dipole-dipole interactions with solvent molecules will lower the


energy of the excited state more than that of the ground state.

• Ethanol solutions give longer wavelengths maxima than do


hexane solutions. i.e. small RED SHIFT (Bathochromic effect),
10-20 nm.
35
n  π*
• This shows a solvent effect on opposite direction.
• The solvent effect is now due to the lesser extent to which solvents can
hydrogen bond to the carbonyl group in excited state.

(CH3)2C==O : n  π*

In Hexane 279 nm, In H2O 264.5 nm


i.e. BLUE SHIFT (Hypsochromic effect)

Searching for a Chromophore

• Bands in visible region Long conjugated or


polycyclic aromatic chromophores.

• One band below 300 nm 2 or 3 conj. Units


36
Auxochrome
A substituent on a chromophores which leads to a redshift.

Another example for Blue shift


Removal of conjugation will result a Blue shift.

+
H2N NH3
H+

230 nm 203 nm

Hypochromic effect – effect leading to decreased absorption intensity

Hyperchromic effect – effect leading to increased absorption intensity


37
Vibrational (IR)
Spectroscopy

38
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

υ – vibration frequency μ – reduced mass 39


Features:
-dipolar moment must change upon vibration
-applicable to solids, liquids and gases
Advantages
-broad applicability
-high sensitivity
-non-destructive technique
Applications:
-determination of bond lengths
-determination of bond force constants
-determination of bond dissociation energy
-qualitative and quantitative chemical analysis 40
Normal Vibration Modes
In general, the description of a molecule
consisting of N atoms requires 3N coordinates.
Three coordinates are necessary to describe the
translational motion of the molecule. The
description of the rotational motion requires
three extra coordinates (two for a linear
molecule).
The remaining 3N – 6 coordinates (3N – 5 for
linear molecules) are used to describe the
motions of the atoms relative to one another, the
so-called vibrational modes.

41
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

42
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

N (H 2O)  3  N vib (H 2O)  3


N (H 2O2 )  4  N vib (H 2O2 )  6
N (C2H 4 )  6  N vib (C2 H 4 )  12
N (HC  C  C  CH )  18  Nvib (HC  C  C  CH )  13

43
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
44
k 1 k
 1 Hz 
2c 
cm1
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:

Ev  v  1 h joules (v  0,1,2,..)


 2

Where ‘’ is the vibrational quantum number. Converting to the


spectroscopic units, cm-1 we have

45
Ev  1  cm1
v   v  
hc  2

as the only energies allowed to a simple harmonic vibrator. Some of


these are shown in the above figure.
In particular we should notice that the lowest vibrational
energy, obtained by putting v = 0 in the equation, is

E0 = ½(h) joules or 0 = ½ cm-1

The implication is that the diatomic molecule (and indeed any


molecule) can never have zero point vibrational energy

46
Applying the selection rule

11/2   
 v 1v  (v  1  1 2 )  v  1 2    cm 1

9/2  for emission


 vv 1   cm 1
for absorption
7/2 
This is because the vibrational
5/2  Levels are equally spaced

3/2 

1/2 

47
The harmonic oscillator is an acceptable approximation only for small
deviation from the equilibrium internuclear distance (vibrations of small
amplitude).

For larger deviations (anharmonicity) the


internuclear potential energy is better
described by a Morse potential:

48
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

Note that the energy levels are no longer equally


spaced. In addition, the number of vibrational levels
is finite: for energies larger than Evmax dissociation of
the chemical bond takes place.
50
The 1H35Cl molecule is quite well described by the Morse potential.
Assuming that the potential De does not change on deuteration, predict
the dissociation energies D0 of 1H35Cl and 2H35Cl.

1 1 2 ~
E v  hc (v  )  x e (v  )  e
 2 2 
D0  De 
E0

Do
D e  5.33eV h  6.6260810 34
Js 1
De
~  2989.7 c m 1
e c  2.997910 8 ms  1
x e~e  52.05 c m 1 1eV  1.60217710 1 9 J

51

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