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CH2209 – Atomic and Molecular Spectroscopy

The Basics of Spectroscopy


Electromagnetic radiation is a wave-like oscillating electric and magnetic field that propagates
through space with a constant speed (c) where wavelength (λ) and frequency (ν) are related by c=λν.

The interaction of these waves with physical matter are the subject of the field of spectroscopy, the
energy provided by a wave will promote shifts within a molecule that are identifiable due to the
quantisation of energy.

The intensity of a spectral transition is due to 3 factors.


i) Transition probability; selection rules explain which transitions are forbidden or allowed and are a
simplified approach as opposed to using much more difficult quantum mechanical calculations
ii) Population of states; transition from the level which initially has the greatest population
(according to the Boltzmann distribution) are more intense

iii) Concentration and path length; the intensity with which radiation is absorbed depends on the
identity of the absorbing species (S), the frequency, the molar concentration ([S]) and the path
length (l) of radiation through the sample.
These properties are connected by the Beer-Lambert law;

[ ]

ε is the extinction coefficient and is dependent on the species and the wavelength at which the
recording is made and so wavelength must be specified for ε. T is the transmittance, the ratio of the
emerging intensity, I, to the incident intensity, I0, and is without units.
The Beer-Lambert law can also be written as;
A=εcl where A is the absorbance.

Quantum Yield - φ
The quantum yield represents the number of molecules of reactant consumed per photon of light
absorbed. If a species absorbs radiation then one particle is excited for each quantum of radiation
absorbed. The measured values of quantum yield range from 10-6 to 106.

-Primary Quantum Yield


For a general photo-process;
A+hν → A* →Products

Here φ cannot exceed unity, i.e. φ≤1, and is a measure of a primary photo-dissociative effect.

-Overall Quantum Yield

When considering the effects of photons on matter it is very possible the excited state formed will
dissociate into free radicals, these are able to then attack the parent molecules and begin a chain
reaction, overall quantum yield is able to take this into account since if φ>1 there must be a
secondary reaction occurring, if φ>2 then a chain reaction must be occurring.

Quenching
There are several paths along which the absorbed energy in a molecule can travel, these include
internal conversion, fluorescence and phosphorescence (as a result of intersystem crossing).

The rate at which the excited singlet state decays can be expressed as;

[ ]
( ) ( ) ( ) ( )
Where kf is the rate of fluorescence, kic is the rate of internal conversion and kisc is the rate of
intersystem crossing.

The lifetime of the species can be defined as;

Quenching is a process by which energy is transferred from the excited molecule, S1, to a quenching
species, Q.

S0+hν→S1 – direct absorption


S1→S0 – direct deactivation (fluorescence, internal conversion, intersystem crossing)
S1+Q→S0+Q* - quenching energy transfer

Now a rate equation can be formed considering the quenching process;

[ ]

Note that quenching is a bi-molecular second order mechanism and so concentration must be
defined.

The quantum yield for fluorescence can be defined as the fraction of molecules that are deactivated
via fluorescence.

Where Σki is the sum of all rates of excited decay, this equation can therefore be expanded as;

[ ]

If the equation for φ1 is divided by that of φ2 the following equation can be formed;

[ ]

Where τ0=1/kf

This is the Stern-Volmer relation which is more often wrote as;

[ ]

ksv is the Stern-Volmer constant and is equal to τ0kq.


The Electronic Spectra of Diatomic Molecules

There are several issues to address when considering the ultraviolet spectrum of diatomic
molecules;
-the number of lines present
-the difference in intensities of lines
-the different spacing between the lines
-the continuum at high energy

These are explained by 3 phenomena, the Born-Oppenheimer approximation, the Franck-Condon


principle and that of dissociation energy.

Born-Oppenheimer Approximation
The total energy of a system can be broken into 3 constituents;

Etotal=Eelectronic+Evibrational+Erotational
The electronic, vibrational and rotational energies are independent of each other , hence they are
uncoupled.

A change in total energy is then written as;

ΔEtotal=ΔEelectronic+ΔEvibrational+ΔErotational

Rotational energy may, however, be ignored as the energies involved are so small
(electronic>>vibrational>>rotational>>translational energy) and so this can be simplified to;

Etotal=Eelec+Evib
-Harmonic Motion
According to the harmonic oscillator
approximation the higher the energy of the
system, the longer the length of the bond
and so the larger the displacement. This
model allows for oscillation to infinity
however which is not realistic, it is well
known that beyond a certain energy a bond
will simply break and so anharmonic motion
is a better descriptor of diatomic molecules.

-Anharmonic Motion
Under anharmonic motion harmonic motion
exists at lower energies however at higher
energy levels the motion tends away from
ideal harmonic oscillation.
This has implications on Etotal.
A new equation can be formed considering the
effect of vibrational energy of this model
including new terms, the vibrational quantum
number (ν), the oscillating frequency (ωe) and
the anharmonicity complex (χe) which ranges
from 0-1, the larger it is the flatter the curve-
off of the energy diagram is.

( ) ( )

This explains why so many lines appear in the


spectra of diatomic molecules, transitions
between different energy levels or progression.
The progressions in a UV spectrum are caused by the superimposed vibrational energy levels in the
molecule. As a result a large number of transitions can occur from the ground to the excited state.

The Franck-Condon Principle


This accounts for the intensity of the lines in the spectrum.
The nuclei in a molecule is subjected to different forces after an electronic transition, an electronic
transition sets up a molecular vibration in an attempt to find the new bond equilibrium distance.
Since nuclei are much larger and heavier than electrons an electronic transition occurs faster than
the nuclei can respond.
The Franck-Condon principle states that ‘electronic transisions occur so rapidly in comparison to
vibrational frequencies that no change in nuclear separation occurs during the course of transition’.

This means that only a vertical transition will give rise to an intense peak, a transition between two
states with the same internuclear separation – electronic transitions occur within a stationary
nuclear framework. The nuclei are defined by their wavefunctions which state where they are most
likely to be found. Since an oscillating object will move fastest at its central point and slowest at the
outer edges of its swing, it is reasonable to state the object will be most likely observed at those
edges. At the lowest possible energy, ν=0, this classical physical theory diverges from quantum
mechanics which in fact states that the nuclei is most likely found in the middle of the motion and
not the extremities.

Here the first, vertical


E’ transition is more intense
than the diagonal transition.

Potential The internuclear distance is


Energy unlikely to change during
electronic transitions (again
due to the mass of nuclei
x x which move much slower
x
than electrons) explaining
this preference for ‘vertical’
transitions.
E’’

x x
x

Internuclear Distance

There is a difference in bond-length between the excited state and the ground state as shown
above, the possible vertical transitions will differ depending on the separation of the parabola.
Since each transition is possible however some more likely, several lines are seen of varying
intensities.
Dissociation Energies and Dissociation Products
Electronic excitation can lead to dissociation in 2 ways;

-bound upper state

E’ O2*

Potential
Energy
DO’
Eex

νcl

E’’ O2 DO’’

Internuclear Distance

DO’’ represents the dissociation energy of the molecule in the ground state and DO’ the dissociation
energy in the first excited state. Since the bond is already weakened in the excited state DO’ is
smaller than DO’’. The energy required to move from the ground state energy to the excited state
dissociation limit is recorded as the frequency of the continuum limit, νcl, and νcl=DO’’+Eex, Eex being
the energy of excitation.

-unbound upper state

E’

Potential
Energy

E’

Internuclear Distance
Estimating the Value of DO’’ and DO’
From vibrational energy levels;

( ) ( )

At the dissociation point ΔE→0 so;

( ( ))

And so;

( )

The answers that this mathematical method give are, however, quite poor. This is since only 2
vibrational levels are considered, more would be required for an accurate approach but also that the
energy levels get closer together at first in a linear trend but one that later becomes curved.

A more accurate approach to assessing the values of DO’ and DO’’ is to use a Birge-Sponer
extrapolation in conjunction with a UV spectrum. By plotting the successive energy change between
peaks against the absolute vibrational quantum level and fitting a curved line the area underneath
will give the value of DO’.

The Fate of Excited Species’

AB → A+B Dissociation PHOTOCHEMICAL


AB → AE+B Direct Reaction
AB → BA Isomerisation
AB → AB++C- Ionisation
AB → AB+CD* Intermolecular energy transfer PHOTOPHYSICAL
AB → AB† Intramolecular energy transfer
AB → AB+hν Luminescence
AB → AB Physical Quenching
Primary Photo-Physical Processes
The term ‘primary photophysical process’ refers to the fate of electronically excited states
proceeding from photon absorption. If subsequent reactions are induced the term ‘primary
photochemical process’ is used.

In luminescence the fate of an electronic molecule is summarized by a Jablonski diagram. The


various stages of the excitation and relaxation are summarized as follows;

1-Photon Absorption
-S0->S1 (singlet, paired electrons, ground state to excited state)
-vibrational relaxation to the lowest ν0 of S1
-excess energy lost as heat
2-Fluorescence
-radiative transition from S1->S0
-fast ‘spin allowed’ transition – electrons do no change spin or angular momentum
-occurs on nanosecond timescale
3-Inter-system crossing
-non-radiative transition from S1->som excited state of T1
-vibrational relaxation occurs to ν0 of T1
4-Phosphorescence
-radiative transition from T1 (ν0) to S0 (ν0)
-slow ‘spin forbidden’ process, electrons cannot change their spin states during the course of the
electronic transition
-occurs on minutes/hours timescale

In a Jablonski diagram a straight arrow shows a radiative transition, a curved arrow shows a non-
radiative loss (heat) and a zig-zag arrow shows a non-radiative iso-energetic transition.

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