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spectroscopy
The Electromagnetic Spectrum
Wavewlength 103 102 101 100 10-1 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9 10-10 1011 10-12
(metres)
Bacteria
Animal cells
Virus
Proteins
Longer H2O Shorter
Tennis ball
wavelength Building wavelength
Generic name
Radio waves Infrared ultraviolet Hard x-rays
Gamma rays
Microwave oven
Microwaves Soft x-rays
X-ray machine
radioactivity
Light bulb
Body heat
FM radio
AM radio
radar
Sources
Frequency (Hz) 106 107 108 109 1010 1011 1012 1013 1014 1015 1016 1017 1018 1019 1020
Energy of
a photon 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-1 100 101 102 103 5 105 106
(ev)
UV/Vis Spectroscopy
IR Spectroscopy
UV/Vis-NIR spectroscopy
UVC 210-280 nm
UVB 280-320 nm
UVA 320-400 nm
Visible 400-700 nm
0.4
0.2
0.0
300 400 500 600 700 800
Wavelength /nm
UV region visible region far red region
Wavelength vs wavenumber 1.4
1.2
1.4
1.0
1.2
0.8
Abs
1.0
0.6
0.8 0.4
Abs
0.2
0.6
0.0
0.4 40000 35000 30000 25000 20000 15000
-1
wavenumber /cm
0.2
0.0
300 400 500 600 700 800
Wavelength /nm
Electronic Absorption
EM radiation has a magentic and an E = hν
electronic vector
singlet triplet
Electronic Absorption
• Total internal energy
Sum of the electronic,
vibrational and
rotational energy
• Etotal = Eelec + Evib + Erot
• For an electronic
transition:
∆Etotal= ∆Eelec+∆Evib+∆Erot
Molar Absorptivity
• Probability that a photon of light will be
absorbed upon passing through an
optically dilute solution
• Proportional to the square of the transition
moment (change in electron density)
• Forbidden transitions
Chromophores & Conjugation
Chromophore – brings colour
The absorption of light is quantised
Mixing of electronic, vibrational and
rotational energy levels leads to broad
spectra instead of lines
C=O C=C
Pigments & Dyes, I
• Retinal – cis/trans isomerisation is the first
step in sensing light
• Chlorophylls absorb light for
photosynthesis
• Types of transitions
n – π* (auxochromes have free electron pairs e.g C=ö: )
n – σ*
σ –σ*
π – π*
Vibrational progression
01
1.0 00 Frank-Condon state
Normaillised absorption and emission
0.8
02
0.6
9,10-di-phenyl-anthracene
0.4
0.2
0.0
28000 26000 24000 22000 20000
-1
wavenumber /cm
The Bougier-Beer-Lambert
Law
An Empirical law – i.e. based on
observation not theoretical
derivation
Transmittance
• The light passing through a sample
• Solvents and optical material are
transparent (100% transmittance) only in
certain regions of the EM spectrum
• Solvent cut-off (see table 7.6, Hesse):
– Water – 190
– CH3CN – 190
– Acetone -350
Transmittance
T = I1/I0
T = 10-A
ε
The Beer-Lambert-Bouguer Law
(empirical law)
• The intensity of light passing through a sample
decreases exponentially and the absorbance of light is
proportional to the concentration of the chromophore
• The absorbance of light is proportional to the pathlength
through which the light travels
A = εcl
A is absorbance, c is concentration (mol L-1), l is pathlength
(in cm) and ε is the molar absorptivity (L mol-1 cm-1)
Isosbestic point
No change in abosrbance
Instrumentation
grating
grating
From: http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/UV-Vis/spectrum.htm
Wavelength vs wavenumber
1.4 1.4
1.2
1.2
In converting from wavelength to
1.0
wavenumber you have to correct for
1.0
0.8 band pass. The slit width is constant in
nm over the whole spectrum but varies
Abs
0.6
in cm-1.
0.8 0.4
Abs
0.2
0.6
0.0
40000 35000 30000 25000 20000 15000
-1
wavenumber /cm
0.4
0.2
0.0
300 400 500 600 700 800
Wavelength /nm
R
0.25
R
0.20
S
0.15 ∆
hv
Abs
0.10 Syn-folded
Anti-folded
S
0.05
R
0.00
R
250 300 350 400
S
Wavelength /nm
Pigments and Dyes II
1.0
0.8
S
S S
0.6
HH hv
H
-H2
H
Abs
0.4
0.2
H H
H H
hv -H2
Isosbestic point
No change in abosrbance
Computational methods
N 2+
ZINDO/S 1 N
ZINDO/S H21 N
Ru
N _N N N
Me N N_ Me
N N N N
Ru
300 400 500 600 700 800 900
N N
N
TD-DFT 1
TD-DFT H21
= 2,2'-bipyridine
N N
MeCN 1
Predicted UV.Vis electronic
MeCN H21
spectra is done on the basis of
an isolated molecule (in
300 400 500 600 700 800 900
vacuo)
H2O 1
H2O H21
However solvent is not
innocent in determining the
absorptivity of chromophores
300 400 500 600 700 800 900
Band Gaps
Semiconductor materials: TiO2 (titanium dioxide –
white paint, some suncreams, solar cells), ITO
(Indium doped SnO2), NiO (nickel oxide)
CB (NiO)
VB (NiO)
Diffuse Reflectance
Brewster’s Angle
Polarisation angle (angle at which light
is fully polarised)
Applications: Following
Reactions
• Isosbestic points
• Multiple reaction steps S
R
0.25
R
0.20
S
0.15 ∆
hv
Abs
0.10 Syn-folded
Anti-folded
S
0.05
R
0.00
R
250 300 350 400
S
Wavelength /nm
Applications: Analysis
• Structural assignments
• Quantitative analysis
– HPLC
– Following reactions