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CH2101 - Spectroscopy
This pdf goes through the basic principles of Spectroscopy, the science of li...
From John
1
1
3
rd
year Spectroscopy
Dr. Alan Ryder (R222, Physical Chemistry)
4 lectures:
–
Rotational & Vibrational spectroscopies
1 exam question.
Notes on:
–www.nuigalway.ie/nanoscale/3rdspectroscopy.html
Spectroscopy links on:
–http://www.nuigalway.ie/nanoscale/links.html
2
3
rd
year spectroscopy:
1
st
Topic
General Features of Spectroscopy:
–Introduction & review of 2
nd
year.–Transitions & probabilities.–Populations of energy levels & consequences.–Linewidths.–Bohr Condition.
Be able to show an understanding of the theories behindspectroscopy. Be able to calculate populations of energy levels andspectral line widths.
–
Section 8.1-2, Physical Chemistry, Atkins 8
th
ed., p.243.
3
Introduction-General Principles
Spectra -transitions betweenenergy states:
–Molecule, E
f
-E
i
= h
ν
(photonenergy).
Transition probability:
–selection rules.
Populations (Boltzmanndistribution).
Molecules have bonds theycan vibrate…
Wavenumber: 5000nm= 5x10
-4
cm= 2000cm
-1
ENERGYPHOTON
BEFORE DURING AFTER
ε ν λ ν
= = =
hhchc
/
∆E (molecule) = E(photon)
4
Absorption spectroscopy
Can refer to the absorptionof any frequency of radiation,most common are:
–UV-visible absorption (
electronic
).–IR absorption (
vibrational
).–Microwave absorption (
rotational
).–NMR/ESR (
nuclear & electron spin
).
These are many types of molecular spectroscopy.
Energy of the radiation
≅
energy of transition.
Based on quantum principles.
2
5
Emission & Scattering spectroscopy
EMISSION:
Emission of anyfrequency of radiation.
Concerned with the propertiesof the emitted photons from asample.
In the UV-VIS-NIR(
electronic transitions
):
–Fluorescence, Phosphorescence,Chemiluminescence,photoluminescence,
In the Microwave:
–Rotational transitions,astrophysics.
Based on quantum principles.
SCATTERING:
Look at howlight scatters frommolecules/materials:
–Not absorbed, photons don’thave to pass thru–Can use everything fromneutrons to x-rays etc.
Most Important is Ramanspectroscopy:
–Molecular technique.–Great for forensics etc.
6
Intensities of spectral lines
Three Essential concepts govern intensity
:
Transition probability
: the likelihood of a system (e.g.molecule) changing from one state to another.
Population of Energy levels:
the number of molecules (oratoms in the initial state).
Concentration (& path length):
The amount of materialpresent giving rise to the spectrum.
–This done last year:
Beer-Lambert
7
Transition probability (I):
Based on quantum mechanical principles…..is a transition
allowed
or
forbidden
?
To simplify matters we use
selection rules
.
Each type of spectroscopy has it’s own selection rules.
Underlying classical idea:
–for a molecule to be able to interact with the EM field andabsorb or create a photon of frequency
ν
,–
it must possess, at least transiently, a dipole oscillating at that frequency
.
8
Transition probability (II):
*z,fiii
ˆ= d .wave function of the initial energy state.= wave function of the final energy state.ˆis the electric dipole moment operator.Rate of change of
fz f z
µ µ τ µ
Ψ ΨΨ =Ψ=
∫
Transition dipole moment:
ffi22ifiz,fi
population of the state (w) due to transitions fromstate is: w || where E = amplitude of EM field, intensity.
The size of the transition dipole can be regarded as a measure o
µ
←←
ΨΨ ∝ Ε ∝
f thecharge redistribution that accompanies a transition.
A transition will be active (and generate or absorb photons)only if the accompanying charge redistribution is dipolar.
3
9
Transition probability (III):
1
s
electron
→
a 2
s
electron:
–Spherical migration of charge.–No dipole moment assoc. with thischarge migration.–Transition is electric-dipole forbidden.
1
s
electron
→
a 2
p
electron:
–Dipole associated with the chargemigration.–This transition is allowed.
10
Gross Selection Rules
Specifies the general features a molecule must have if it isto have a spectrum of a given kind:
–e.g. a molecule gives a rotational spectrum only if it has apermanent electric dipole moment.–e.g. a vibration is Raman active only if there is a change inpolarizability.
A detailed study of the transition moment leads to the
specific selection rules
that express the allowedtransitions in terms of the
changes
in
quantum numbers
.
11
Populations of energy levels (I)
The strength of an absorption depends on the number of moleculesin a particular energy level.
Governed by the Boltzmann Distribution:
i
i ii
-/kT
N= no. molecules in an energy level, , with energy E.N = total no. molecules iNeBoltzmann distn system.Taking into account degenerate energy lribution: N=e vels,,
E
q = partition functioniq
i
-/kTi ii
we can write:N ge at equilibrium,where gnumber of degenerate levels.
E
∝ ×=
12
Populations of energy levels (II)
In spectroscopy:
–interested in the relative populations of energy levels.
iif i
i iiiiffff iiiii
-/kT-/kT-/kT-/kT
N ge at equilibrium, where gnumber of degenerate levels.NegNNgNgeexp(()/)NgNgeN=rearrano.nge to:
fi
E E E E
ratio, q = partition functionqratio,EEkT,
∝ × =
⇒
= = ×
⇒
= = × = × − −
iff
f i
molecules in an initial energy level, , with energy E.N= no. molecules in a final energy level, , with energy E.So assuming single states:
Nexp(()/)N
i f
final state EkT,initial state
= − ∆
of 00
3rd Year Spectroscopy
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