Molecular Spectroscopy

SCES/P2250

Main Reference: Fundamentals of Molecular Spectroscopy

Colin N Banwell and Elain M McCash
Fourth Edition
Tata McGraw-Hill Publishing Company Limited

Reference book is imperative. Notes will refer to the book .

Proforma of Molecular Spectroscopy Course

Fakulti : Sains
Jabatan : Kimia

Program B.Sc. (Hons.)

Pengajian :

Kod Kursus : SCES2250

Tajuk Kursus : Spektroskopi Molekul
Jam Kredit : 3

Prasyarat / Kimia Fizik II

Keperluan Minimum
Kursus :

Objektif Kursus : Memberikan kefahaman tentang spektroskopi

molekul sebagai alat utama untuk memahami
struktur molekul dan sifat-sifatnya
Sinopsis Kandungan Spektroskopi putaran, getaran dan
Kursus : elektronik.
Spektrum elektromagnet. Asas-asas
spetroskopi. Spektrum putaran dan getaran
molekul dwiatom dan poliatom. Kesan Raman;
spektrum Raman putaran dan getaran.
 Keadaan elektron dalam molekul; teori
kumpulan asas untuk spektroskopi, pencirian
keadaan elektron (term symbols). Peralihan
elektron, spektroskopi elektronik, momen
dwikutub peralihan. Pendafluor dan
pendafosfor.

Spektroskopi resonans magnet

Sifat magnet elektron dan nucleus. Kelakuan
electron dan nucleus dalam medan magnet:
pengkuantuman momentum sudut, tenaga spin,
taburan Boltzmann spin, pemagnetan
makroskopik. Resonans magnet dan
eksperimen. Parameter spectrum NMR:
anjakan kimia, pengkupelan spin-spin dan
masa relaksasi nucleus (T1 dan T2). Faedah
medan magnet tinggi. Resonans dubel. Kesan
relaksasi dan resonans dubel ke atas
spectrum NMR karbon-13. Masa relaksasi T1
dan maklumat gerakan molekul. Kelakuan
nukleus kuadrupol sebagai nukleus tak-
magnet. . Skala-masa NMR; kesan fenomenon
pertukaran ke atas spectrum NMR. Prinsip
asas bagi NMR bagi keadaan pepejal, NMR
dua-dimensi dan NMR mengimej.

Kaedah Penilaian : Penilaian berterusan: 30%

Peperiksaan: 70%

English Version

Faculty : Science
Department : Chemistry

Course B.Sc. (Hons.)

programme:
Course code: SCES2250/2132/SCEP2132/SCES2235
Course title: Molecular Spectroscopy
Credit hours: 3

Pre-requisite: Physical Chemistry II

Course objective: To give a fundamental understanding of

molecular spectroscopy as the most important
tool in understanding molecular structure and its
characteristics
Synopsis of Vibration, rotation and electronic
course content: spectroscopy.
Electromagnetic spectrum. Fundamentals of
spectroscopy. Rotational and vibrational spectra
of diatomic and polyatomic molecules. The
Raman effect; rotational and vibrational Raman
spectra. Elementary group theory for
spectroscopy. Electronic states in molecules and
term symbols. Electronic transition, transition
dipole moment and electronic spectra.
Fluorescence and phosphorescence.

Magnetic resonance spectroscopy.

Magnetic properties of the electron and nucleus:
spin angular momentum and magnetic moment.
Behavior of electron and nucleus in magnetic
field: space quantization of angular momentum,
spin energy, Boltzmann distribution and
macroscopic magnetization. Magnetic resonance
and experiment. Parameters in the NMR
spectrum: chemical shift, spin-spin coupling and
nuclear relaxation time (T1 and T2). Advantages
of high magnetic field. Double resonance.
Effect of nuclear relaxation and double
resonance on carbon-13 NMR spectra.
Relaxation time T1 and molecular motion.
Behavior of quadrupolar nuclei as non-magnetic
 nuclei, NMR time-scale; effect of exchange
phenomena on NMR spectra. Basic principles of
solid-state NMR, two-dimensional NMR and NMR
imaging.

Grading: Continuous assessment: 30%

Examination: 70%

Other references:

1) Modern Spectroscopy
J. Michael Hollas
Second Edition
Wiley

2) Molecular Spectroscopy
John M Brown
Oxford Science Publications

3) Physical Chemistry
P W Atkins
Oxford

Other Spectroscopy/Physical Chemistry books available in the library

1 Introduction to Spectroscopy

1.1 Electromagnetic Spectrum

Molecular spectroscopy may be defined as the study of the interaction

between electromagnetic waves (EMW) and matter (atoms or molecules).

When matter (molecules) absorb EMW, the molecules can undergo changes.
These are broadly classified as: 1) rotation 2) vibration 3) redistribution
of electrons.

The three types of changes occur when molecules absorb EMW of differing
energies.

1.2 What is EMW? (pg. 1-3)

EMW of which visible light forms an obvious but very small part may be
considered as a simple harmonic wave propagated from a source and
traveling in a straight line except when refracted or reflected.

Diagram1.1: EMW

EMW applet
http://mutuslab.cs.uwindsor.ca/schurko/animations/emwave/emwave.htm

EMW consists of electric field and magnetic field parts; both waves are
perpendicular to each other.

Q1: Write the equations of EMW:

Basic wave equation is c/ where  is the wavelength in meters, c is the

speed of light in ms-1 and  is the frequency in Hz (cycles s-1). In
spectroscopy, a widely used unit is the wavenumber (cm -1), giving a
generalized connotation of energy, frequency etc. This is defined as:
ν=1/λ
Using appropriate units for c (cms-1) and  (cm), it would be easy to convert
from Hz to wavenumber and vice versa. A bar above  indicate units in cm-1
 Q2: Convert – 133MHz to cm-1, 400cm-1 to Hz, 300nm to cm-1

1.3 EMW spectrum (pg. 5-9)

To answer the question concerning the types of interaction that will occur
when molecules absorb EMW, we need to understand that EMW exists in
different energies. This can be conveniently expressed in terms of an EM
spectrum.

Visible light spectrum

Understand the EM spectrum presented (see a more lively EMW spectrum –
in folder). Make sure you develop the sense of magnitude related to the
spectrum. It is imperative that you understand, for example that EM in the
microwave region, when absorbed by a molecule will cause the molecule to
rotate.

Q3: Write brief notes on the EM spectrum and how it interacts with
matter:

1.4 Quantization of Energy (pg. 3-5)

Initially matter was thought to be able to absorb energy in the form of

EMW continuously, soaking up all the energy available over the whole
spectrum of EMW. This was found to be incompatible with reality. Max
Planck published a revolutionary paper suggesting that energy of an
oscillator is discontinuous and change of energy can happen by means of a
jump between two energy states.

Extending this idea, a molecule can also be thought to possess energy in

quantized form – rotation, vibration, electronic.
Etotal = Erotation + Evibration + Eelectronic (ET = Er + Ev + Ee )

This is known as the Born Oppenheimer approximation.

Matter absorbs EM energy in a quantized manner. Best visualized via energy

level diagram:
Diagram1.2 : Transitions between two energy levels

Upon absorption of EMW of a certain energy, a transition is said to occur. It

is then said that the matter has absorbed a photon of EMW. This transition
can be described by an equation suggested by Planck.
ΔE=hν s
Where E = En-Em.

ν s is the frequency absorbed. This is in Hz. The symbol for frequency in

cm-1 is usually ν s unless different symbols are noted to have units of cm-1.

If we plot a graph of intensity of absorption vs. frequency, we get a

spectrum with a peak at
νs .

Three types of transitions are shown in diagram1.2. What are they?

Q4: Draw a spectrum with absorption at ν s .

In spectroscopy we can envisage the quantized energy levels as depicted
below:

Diagram1.3 : Magnitude of the different type of energy levels

The physics that deals with quantized energies of molecules is quantum

mechanics. The basis of quantum mechanics is the Schrodinger equation.
Solution to this equation basically gives two things. Energy (levels) (E) and
wavefunctions (Ψ) associated with each energy levels.

As an example, lets jump straight into a real case – the hydrogen atom. A
Schrodinger equation for the kinetic and potential energy at play within the
atom which consists of an electron and a proton is set up. It is then solved
to give energy levels and wavefunction. These wavefunctions are
appropriately combined to result in atomic orbitals.

Thus, we have 1s, 2s, 3s, 2p etc. atomic orbitals (which are really
combination of wavefunctions from the solutions of the schrodinger
equation). Each orbital is identified with an energy level represented (or
labelled) by its quantum number.

The details of this can be obtained from various Physical Chemistry texts.

Since hydrogen atom is an atom, the only energy it possesses is the

electronic energy (besides the continuous translational energy). Absorption
of EM in the region of UV/Vis will cause electrons to be excited from one
level to another, corresponding to the energy absorbed.

A molecule, such as A-B on the other hand will have rotational and vibrational
energy besides electronic energy.

Q5: Why do atoms lack rotation and vibrational energies?

Upon absorption of EM by a molecule, we ask three questions:

1) The frequency of absorption

2) The line intensity
3) The linewidth of the spectral line.
The frequency of the absorption can be read off the spectrum and the type
of interaction depends on the value of the frequency (sense of magnitude?
EM spectrum?)

Q6: Draw a single line spectrum and illustrate the spectrum with labels
appropriate to the three questions:

Questions 2) and 3) will be answered below.

1.5 Spectral line intensity (pg. 18-20)

Spectral line intensity is determined basically by three factors:

a) Transition probability – A rigorous quantum mechanical treatment of

EM-matter interaction will produce what is known as the transition
probability. It is represented by:

Rnm =∫ ψ n∗⃗μ ψ m dτ
n m
Where ψ and ψ are wavefunctions of states n and m
respectively. ⃗μ is the electric dipole moment operator. The spectral
 line intensity is proportional to Rnm2. If Rnm = 0 then there is no
transition (forbidden), whereas if Rmn <> 0, there can be a transition
(allowed). This is also known as the gross selection rule for a
transition. The transition probability will be rationalized later for
each type of transition; rotation, vibration and electronic.

b) Population of states – between two states, if the lower state is of

higher population, and the upper one is lower in population, then the
transition is very much favoured. Boltzmann distribution determines
the relative population. Understand this properly. This will be
discussed further for each type of interaction

Q7: Write the Boltzmann distribution population ratio of two states m

and n

c) Concentration of sample or path length of sample – works within the

Beer Lambert Law:

log Io/I = cl

Where I is the transmitted light intensity, I o is the incident light

intensity, c is the concentration of sample, l is the path length and  is
molar absorption coefficient ( a function of frequency).
Good applets on this can be obtained from :

http://www.chm.davidson.edu/ChemistryApplets/#Spectrophotometr
y

1.6 Spectral linewidth (pg. 17-18)

There are 3 factors that effect line broadening:

a) Natural linewidth – Heisenberg uncertainty principle. This is natural in
all spectroscopic measurements.

1
Δν=
2 πτ

There will always be broadening because  can never be infinite.

Broadening due to only one frequency – homogeneous spectral line

b) Doppler broadening – due to Doppler shift – based on Doppler effect

Diagram1.4 : Doppler effect

As an example: Sound waves emanating from an ambulance moving to the

right. The perceived frequency is higher on the right, and lower on the
left. Imagine molecules as source being stationary, or moving relative to
the detector. Molecules move randomly – as a result, you get many
different frequencies centred around a mid frequency, each frequency
overlapping with each other forming a gaussian envelope – heterogeneous
spectral line. Doppler effect applet-
http://www.phy.ntnu.edu.tw/java/Doppler/Doppler.html

c) Pressure broadening (collision broadening)

Due to continuous collision between molecules/atoms. This causes

perturbation to the energy levels, thus broadening it – more severe in
 liquid. Can be reduced by taking spectrum in gas phase and lowering the
pressure of gaseous samples

2 Representation of Spectra – practical aspects of spectroscopy

(pg. 9-17)

There are basically 3 types of spectroscopy experiments:

1) Absorption
2) Emission
3) Scattering

Absorption spectrometer applet:

http://artsci-ccwin.concordia.ca/facstaff/a-c/bird/c241/D2-part2.html
We shall only look into the first two at the moment.

2.1 Absorption

- UV/Vis, IR (optical) and microwave (non-optical)

Q8: Draw the complete diagram of a basic optical absorption experiment

complete with appropriate labels and explanation of the labels.
2.2 Emission

- UV/Vis (optical)

Q9: Draw the complete diagram of a basic optical emission experiment

complete with appropriate labels and explanation of the labels.
Diagram 1.4a – typical arrangement of an absorption spectrometer

Among the important parts of the spectrometer are:

1) Source – the types of sources will depend on the types of interaction

desired (refer to handouts).
2) Slit – used to direct EMW to sample or to determine resolution.
Unfortunately, slits also reduce the total intensity that could have
been utilized.
3) Dispersing element or a grating – used to disperse EMW into its
constituent frequencies. Used in conjunction with a slit (see handout).
This part of the spectrometer is usually called a monochromator
(below). An applet demonstrating the action of a grating can be found
at:

http://www.mtholyoke.edu/~mpeterso/classes/phys301/laboratories/balmer
.html
http://www.physics.uq.edu.au/people/mcintyre/applets/optics/grating.html

Diagram1.5 : Monochromator (action of a grating)

4) Sample holder – to hold sample – quartz and glass (UV/Vis), KBR, NaCl
salt slabs (IR) – depending on the EMW region
5) Detector – types of which are determined by the different EMW
sources – see handout
6) Display – displays the spectrum – computers, chart recorders.

We should also consider the two types of operation in a spectrometer –

single beam and double beam operation – this is done in order to compensate
for the background which may affect the spectrum due to the presence of
water vapour and carbon dioxide absorption. This is especially true for IR
spectroscopy (pg. 91-93) – See brochure of Lambda series of spectrometers.

2.3 Signal to Noise Ratio (pg. 15)

Modern electronic instruments can’t escape from noise. The noise can come
from the electronic cricuitry in the spectrometer or from the detector.
Noise is usually described in termso fluctuation. To differentiate between
signal and noise, we need the signal to be at least 3 or 4 times larger than
noise.
Signal-to-noise ratio is an engineering term for the power ratio between a
signal (meaningful information) and the background noise:

Because many signals have a very wide dynamic range, SNRs are often
expressed in terms of the logarithmic decibel scale. In decibels, the SNR is
20 times the base-10 logarithm of the amplitude ratio, or 10 times the
logarithm of the power ratio:

where P is average power and A is RMS amplitude

There are various techniques to increase S/N ratio such as filtering and
computer averaging (pg. 26).

2.4 Spectral resolution (pg. 16)

Often used as a mesure of the performance of a spectrometer.

Q10: Explain how the size of the output slits can affect the resolving power
of a spectrometer. Use appropriate illustrations.
2.5 Fourier Transformation in Spectroscopy (pg. 20-26),(pg. 93-96)

Conventionally a spectrum is taken by sweeping over the whole range of

frequencies within the spectral domain. Say, a spectrum from 1000cm -1 to
4000cm-1 is to be recorded. The frequency is swept smoothly from 1000 to
4000cm-1 (by rotating the grating in the monochromator). This takes a long
time. Very inefficient. With FT technology, the whole spectrum can be taken
simultaneously within the required region. To understand FT, first look at
beat frequency. Visit:

http://www.ithacasciencezone.com/explrsci/dswmedia/tonebeat.htm
http://physics.pingry.org/Explorations/Acoustics/Beats/

for audio demonstration of beat frequency.

300Hz

+
about 300Hz (say 301 Hz)
gives….
….a beat frequency.

..which is an interference pattern. Imagine interfering more than 2

frequencies, in fact imagine interfering hundreds of frequencies together.
Conceptually, a combination of many different frequencies will result in a
particular interference pattern. This pattern is in time domain (serial
domain). You can’t tell what the different frequencies are…we have to
convert this interference pattern into a frequency domain spectrum where
interfering frequencies can be identified – FT!!

Note that an interferogram shows an oscillating signal decaying smoothly to

zero. The oscillation is due to the beat pattern set up by all the
superimposed, but slightly different sine waves emitted. The decay can be
imagined by considering that initially, all waves in the package are in step but
as time goes by they start to be out of phase that on average, they cancel
out (pg.22-23)

Good applets to demonstrate time domain to frequency domain using FT..

http://storm.uni-mb.si/CoLoS/applets/fft/ftd.html
http://sepwww.stanford.edu/oldsep/hale/FftLab.html

By using an interferometer, we can take the spectrum instantaneously and by

using FT, the interferogram is transformed into a frequency domain
spectrum. Read about the interferogram and understand how it works.

A typical arrangement of an FTIR is depicted below (diagram 1.6). How does

it work?

Diagram 1.6 : FTIR

Demonstration of Michelson interferometer.

http://www.physics.uq.edu.au/people/mcintyre/applets/michelson/michel.ht
ml

Tutorial:

1) Convert 99.3MHz, 103.3MHz, 105.9MHz dan 2.4GHz into wavenumber

(cm-1).
2) Which region of the EMW causes molecular rotation? What are the
selection rules required in order to observe rotational spectrum?
3) A molecule X absorbs EMW at 3500cm-1. What happened to it?
4) Electron redistribution in a molecule or atom occurs in the EMW
region of….
5) Draw the diagram of a simple absorption spectrometer and explain the
workings of this apparatus
6) What is the function of the first dispersion element of an emission
spectrometer (in the monochromator before EMW enters the sample?
7) Give example of the source of EMW for each identifiable region of
the spectrum.
8) Write down the energies of a molecule based on the Born
Oppenheimer approximation.
9) List down the factors that influence the intensity of a spectral line
10)Discuss the three types of spectral line broadening
11) Discuss how an FTIR spectrometer works.
12)Explain why the natural linewidth in a rotational spectrum is smaller
that the natural linewidth of a UV spectrum?
13) What is S/N ratio?
14) What is Rmn?