UV-VIS Absorption spectroscopy

(Electronic spectroscopy)

The earliest method of molecular spectroscopy!

Absorption of photon results in electronic transition of a molecule.

(electrons are promoted from ground state to higher electronic states)

Quantitative Analysis / Qualitative Analysis

a. Transitions between electronic energy levels are induced by EMR in the UV-
visible region.
250 nm = 40,000 cm-1 = 1.2 x 1015 Hz = 480 kJ/mol
b. Within each electronic state are a series of vibrational and rotational levels.

c. The relative populations of the various states are governed by Boltzmann

distributions:
n2   (E 2  E1 ) 
 exp  ; k  1.38 x 1023 J/K;
n1  kT 

d. At room temperature nearly all molecules are in the vibrational ground state.
e.g., for E = 10 kJ/mol, N2/N1 = 0.0176 at 298 K
e. Electronic transitions can occur to various vibrational-rotational states in the
excited electronic state. (The spectrum for a given electronic transition should
consist of a large number of closely spaced lines.)
In practice, this is observed only in dilute gases or at very low temperatures.

In solution, at room temperature, the fine structure is lost due to collisions,

environmental heterogeneity, Doppler shifts, etc.

f. The electronic energy can be modeled as a harmonic

oscillator near the equilibrium bond distance.

g. The nuclei are fixed on the timescale of the

electronic transition (Franck-Condon Principle:
electronic transitions are vertical).
 Quantitative Analysis

UV-Vis spectroscopy is used more for routine analytical determinations .

For concentration determinations Beer-Lambert law is used:

A = ε·b·c
b = the length of light path through the sample (cm).
c = the concentration of the compound in solution (mol/L),
ε = the molar absorptivity (L·mol-1·cm-1),
A= the absorbance, (A = log(I0/I)).
 For concentration determinations the calibration curve can be used (already
existing or determined in the laboratory).
To build a calibration curve
the absorption spectra for
different concentrations of a
solution of the same substance
are recorded.
The intensity of absorption
bands is determined and then is
plotted the absorbance
(maximum of absorption) versus
concentration: A = f (c).
According to the Beer-Lambert Law,
absorbance is proportional to concentration,
and so you would expect a straight line.

The Beer-Lambert Law breaks down for

solutions of higher concentration.
The Beer-Lambert law is additive:
Absorbance of a mixture, at a certain wavelength, is the sum of each component
absorbance at the considered wavelength .
To determining the concentration of a mixture of two or more substances, UV-
Vis absorption spectra of each component is needed (for a known concentration).
Usually, the number of wavelength used to determine the absorbances is equal
with the number of the constituents from mixture.

One option is to choose those wavelengths at which each component has the
maximum of absorption.

A ( x1  y )  A x1  A y1   x1 bc x   y1 bc y

A ( x2 y )  A x 2  A y 2   x 2 bc x   y 2 bc y

By solving the system the concentrations (cx, cy) of the two components of the
mixture can be determined.
Absorption spectrum = the dependence of
absorbance from wavelength: A = f(λ).

From the absorption spectrum can be

determined:
- the position of the absorption maxima
- the intensity of the absorption maxima

Absorption curve is influenced by

- Temperature (at higher temperatures monomers are predominant)
- Concentration (at higher concentrations dimers/polymers are predominant)
- pH (influencing the balance between ionized and non-ionized forms)

- izobestic point is the intersection of

all absorption curves of a solution at
different pH's
dI
 cdl
I
I dI l
Io I   0cdl
I
ln  cl
Io
Io
 log   log T  2.303  cl
I
A  lc

A = ε·b·c

A - absorbance
b - length of light path through the sampl
c - sample concentration
ε - molar absorptivity
The amount of absorbed radiation may be measured in a number of ways:

- transmittance T = I/I0 = 10-ε·b·c %T: [0%,100%]

- absorbance A = lg(1/T) = ε·b·c A: [0,∞)

If all the light passes through a

If all the light is absorbed, then solution without any absorption,
percent transmittance is zero, and then absorbance is zero, and
absorption is infinite percent transmittance is 100%.
 Transmitance Absorbance

Molar absorptivity is a constant for a particular substance (at a wavelength).

 Limits to Beer’s Law: Chemical Deviations

- high concentration:
- particles too close
- average distance between ions and molecules are diminished
- affect the charge distribution and extent of absorption.
- cause deviations from linear relationship.

- chemical interactions: dissociation or reaction with the solvent

 Limits to Beer’s Law: Instrumental Deviations

－non-monochromatic radiation: deviation of calibration curve from linearity

－stray light (policromatic light): if a significant

amount of the light passed through the sample
contains wavelengths that have much lower
extinction coefficients than the nominal one, the
instrument will report an incorrectly low absorbance.
 Limits to Beer’s Law: Experimental Deviations

- reflections, scattering, etc. modify the reported absorption.

 Instrumentation

Light Source
Deuterium Lamps－a truly
continuous spectrum in the
ultraviolet region is produced by
electrical excitation of deuterium at
low pressure. (160nm~375nm)
Deuterium Lamps

Tungsten Filament Lamps－the

most common source of visible and
near infrared radiation.
 Monochromator
• The diffraction grating splits light into its component colours.

• The exit slit allows only light of a very narrow range of wavelengths into the
rest of the spectrometer.

• By gradually rotating the diffraction grating, the light from the whole
spectrum (a tiny part of the range at a time) reach into the rest of the
instrument.
 Detector

The Photovoltaic Detector measures the

intensity of photons by means of the voltage
developed across the semiconductor layer.
Electrons, ejected by photons from the
semiconductor, are collected by the silver
layer. The potential depends on the number
of photons hitting the detector.

The Phototube Detector is a vacuum

tube with a cesium-coated photocathode.
Photons of sufficiently high energy hitting
the cathode can dislodge electrons, which
are collected at the anode. Photon flux is
measured by the current flow in the system.
 The Photomultiplier Detector consists of a photoemissive cathode coupled with
a series of electron-multiplying dynode stages.

The primary electrons ejected from the photo-cathode are accelerated by an

electric field so as to strike a small area on the first dynode.

The impinging electrons strike with enough energy to eject two to five secondary
electrons, which are accelerated to the second dynode to eject still more electrons.

A photomultiplier may have

9 to 16 stages, and overall
gain of 106~109 electrons
per incident photon.
 Single and Double Beam Spectrometer

• Single-Beam: There is only one light beam or optical path from the source
through to the detector.

• Double-Beam: The light from the source, after passing through the
monochromator, is split into two separate beams: one for the sample and the
other for the reference.
Photodiode array (CCD)
allow simultaneous
detection of all wavelength.

No monochromator is
needed!
 Sample cell

The sample and reference cells are small

rectangular containers made by:
- glass (using over Visible region)
- quartz or fused silica (Using over 190 nm)

The cell are often designed so that the light beam travels a distance of 1
cm through the contents (1 mm for low volume).

The sample cell contains a solution of the substance - usually very

dilute.

The solvent is chosen so that it doesn't absorb any significant amount

of light in the wavelength range we are interested in (200 - 800 nm).

The reference cell just contains the pure solvent.

 Qualitative analysis

Absorption of electromagnetic radiation in the UV-VIS range change the

distribution of electrons in the molecule.

Internuclear distances and force constants corresponding to the excited

and ground electronic states are different!
 UV-Vis spectroscopy corresponds to electronic transitions between energy
levels of molecular orbitals. (UV = 200nm - 400 nm, Visible = 400 nm - 800 nm)

The frequency of absorbed light (wave number, wavelength) depends on the

structure of the molecule and on its neighborhood.
 Different molecules absorb different wavelengths of radiation.

Absorption spectrum consists of absorption bands corresponding to

structural groups of molecules (Chromophores)

The color arises when a molecule absorbs certain wavelengths

of visible light and transmits or reflects others.

The chromophore is a region in the molecule where the energy

difference between two different molecular orbitals falls within the range of
the visible spectrum.

Visible light that hits the chromophore can thus be absorbed by exciting
an electron from its ground state into an excited state.
In the absorption spectrum of molecules that contain more chromophore,
the folowing changes can occur due to interaction of the chromophores:

Hypsochromic shift, (λmax↓) Bathochromic shift (λmax↑)

Hypochromice effect (abs. ↓) Hyperchromic effect (abs.↑)
 A diatomic molecule may undergo electronic, vibrational and rotational
transitions.

The Born-Oppenheimer approximation (“Since the energies of the

various motions are very different, motions of a diatomic molecule may be
considered as independent”) allows us to express the total molecular
energy as:
Etot = Eelec + Evib + Erot

As a result of a transition, the change in the total energy of a molecule is:

ΔEtotal = ΔEelec + ΔEvib + ΔErot

(the approximate orders of magnitude: ΔEelec ~ ΔEvib ∙ 103 ~ ΔErot ∙ 106 )

Unlike in vibrational and rotational spectroscopies, all molecules

give electronic spectra.
Vibrational changes produce a “coarse structure” and rotational changes a
“fine structure” on the electronic transitions.

S0→S2 S0→S1
Vibrational "coarse" structure: 1 1
E total  E elec  hc[(v  )  e  x e ( v  ) 2  e ]
2 2

X - electronic ground state (S0),

A - electronic excited state (S1),

(") - lower state;

(') - higher state

generally: v” ≠ v’

For vibrational transitions between different electronic levels, there

is no rule for Δv, so that every v" → v' transition has some
probability, giving rise to many spectral lines.
 Absorption spectra from the ground state are more likely: virtually all the
molecules are in their lowest vibrational state (v” = 0), so that the only transitions
we observe are (0, 1), (0, 2), (0, 3) etc.

Each set of transitions in a band is called a v’ progression, since the value of

v’ increases by unity for each line in the set.

The lines in a band are closer together at high frequencies because of the
anharmonicity of the upper state vibrations, which causes vibration energy levels to
converge.

In general, the spacings of vibrational

energy levels in the two electronic states are
different.
 Example:
The vibrational-electronic spectrum of I2 in the region from 500-650 nm displays a large number of well-
defined bands which, for the most part, correspond to 0  v' transitions connecting the v" = 0 vibrational level of the
ground electronic state to many different vibrational levels v' of the excited electronic state. Under the conditions of this
experiment (i.e., low resolution), the rotational lines within each band are not resolved.
Each small peak, such as the (26,0) band labelled on the spectrum, corresponds to a transition between two
vibrational levels and is called a band. Each band is comprised of several hundred lines, each of which involves
different upper and lower rotational quantum numbers; as mentioned, these lines are not resolved in the present
experiment. The region of maximum absorption in each band is caused by many of these lines falling together; it is
called the band head. The set of all of these bands is referred to as the visible band system of I2

If the sample is hot, then excited vibrational

levels of the ground state may be populated, and
these also will absorb light.
The hot bands arising from absorption from
v"=1 and v"=2 are shown very approximately on
the absorption spectrum above.

At a point called the convergence limit, the

spacing between bands decreases to zero.
Beyond this convergence limit, the spectrum
is continuous because the excited state of the
I2 molecule is not bound.
The change in the total energy is: ΔEtotal = ΔEelec + ΔEvib

1 1 1 1
E total  E' elec E"elec hc[(v' )  ' e x ' e ( v' ) 2  ' e ( v" ) "e x"e ( v" ) 2 "e ]
2 2 2 2
If a sufficient number (at least five) of lines can be resolved in the band, the
values: x'e, x"e,  'e , "e and (E’elec – E”elec) can be calculated.

For a given electronic transition: E'elec- E"elec = ΔEelect = constant.

1 1 1 1
ΔEtotal  ΔEelec  hc[(v'  )ν'e  x' e(v'  )2 ν'e (v"  )ν"e  x" e(v"  )2 ν"e ]
2 2 2 2

Considering only the terms (G(v') = ΔEtotal/hc) from a progression (ex. v"= 0)

1 1 1 1 1
G( v' )  E elec  [(v' )  'e x ' e ( v' ) 2  ' e ( ) "e x"e ( ) 2 "e ]
hc 2 2 2 2
and makes the difference between two consecutive terms, will obtain an
expression which is a first degree equation in (v'+1/2):
1 1
G  G( v'1)  G( v' )   'e 2x 'e  'e ( v' )  f ( v' )
2 2
If we represent ΔG = f(v’ +1/2) will obtain the Birge-Sponer line.
The slope of this line is equal to: 2x' e  'e
1 1
G  f ( v' )   'e 2 x'e  'e ( v' )
2 2
The y intercept represent  ' e (the vibrational frequency of harmonic oscillator).
The x intercept represent the number of vibrational levels from the electronic excited
state: v'max
If the terms from a series are used, the values corresponding to (") state will be
obtained.
The area below Birge-Sponer line represent the dissociation energy D0.

De energy is the maximum value of G (v):  e2

D e  G max v  
4  e  x e
 Vibrational band analysis: the Deslandres table

In order to draw Birge-Sponer line the Deslandres table could be used.

The Deslandres table contain vibrational wavenumbers of electronic transitions
and the differences between them.

The differences between rows and

columns is constant, and correspond to
the energy difference between a
particular pair of vibrational levels in
either the upper state (rows) or the lower
state (columns):
Intensity of vibrational-electronic transitions (vibronic):
The vibrational lines in a progression are not of the same intensity. Intensities of the
vibrational bands are determined by three factors:

(1) The intrinsic strength of the transition

(2) The populations of the levels involved.
(3) The overlap of the vibrational wavefunctions (the Franck-Condon factor).
The Franck-Condon principle:
“Since electronic transitions occur very rapidly (≈ 10-15 s), vibration and
rotation of the molecule do not change the internuclear distance appreciably during the
transition”.
The intensity of a transition is greatest for the largest of the vibrational
wavefunctions.
In view of the Franck-Condon principle, electronic transitions occur “vertically” on
a
potential energy diagram.

Franck-
Condon principle →
explains the intensity
of vibronic transitions

An electronic transition
occur without changing
the position of nuclei in
the molecule.
(1) If the internuclear distances in the upper and lower states are equal (re” ≈ re’),
the most probable transition is (0, 0) (left). However, there is a non-zero probability of
(1, 0), (2, 0), (3, 0) etc. transitions. The successive lines will therefore have rapidly
diminishing intensities.

(2) If the excited electronic state has a slightly

larger nuclear separation than the ground
state (r'e > r"e), the most probable (and thus
most intense) transition is (2, 0) (center).
The intensities of the neighbouring transitions
are lower.

(3) When the excited electronic state has a

considerably larger nuclear separation than
the ground state (r'e >> r"e) (right), the
vibrational state to which the transition takes
place has a high v’ value.
Further, transitions can occur to levels where
the molecule has energy in excess of its
dissociation energy.

From such states the molecule will dissociate without any vibrations and, since the
fragments which are formed may take up any value of kinetic energy, the transitions
are not quantized and a continuum results.
Types of electronic transitions:

A. Transitions involving electrons π, σ and n

B. Transitions involving charge transfer The electronic structure of CH2O
C. Transitions involving electrons d and f

A. Organics: Involving π, σ, n electrons

Saturated compounds
σ→σ* (<150 nm), n →σ* (<250 nm): deep UV
Double bonds/unsaturated systems
less energy to π∗
π→π*, n →π* transitions: (200-700 nm)

B. Metal-ligand complexes: charge transfer

transition
Electron moves between ligand and metal.
One must act as donor and other as acceptor.

C. Inorganics: d-d transition

Additionally, transitions between d orbitals
split by presence of ligand field.
Usually in visible.
Molecular orbital theory (MO):

An atomic orbital is the space within

which an electron belonging to the orbital
spends 95% of its time.

In molecular orbital theory orbitals

embrace two or more nuclei.

Electrons in a molecule are not tied to

a particular atom, they are "scattered"
throughout the entire molecule.
 The lowest energy transition (and most often obs. by UV) is typically that of
an electron in the Highest Occupied Molecular Orbital (HOMO) to the Lowest
Unoccupied Molecular Orbital (LUMO)

For any bond (pair of electrons) in a molecule, the molecular orbitals are a
mixture of the two contributing atomic orbitals; for every bonding orbital “created”
from this mixing (σ, π), there is a corresponding anti-bonding orbital of
symmetrically higher energy (σ*, π*)

σ-orbilals: typically are the lowest energy occupied orbitals; the

corresponding anti-bonding (σ*) orbital is of the highest energy

π-orbitals are of somewhat higher energy, and their complementary anti-

bonding orbital (π*) somewhat lower in energy than σ*.

n-orbitals: non-bonding electrons lie at the energy of the original atomic

orbital, most often this energy is higher than π or σ (since no bond is formed, there
is no benefit in energy)
*
p* Unoccupied levels
Atomic orbital n Atomic orbital
p Occupied levels

Energy Molecular orbitals
Molecular orbital wavefunction is a linear combination of atomic orbital wavefunctions.

For bonding orbitals the interference between the two atomic orbitals are constructive.
For unbonding orbitals the interference between the two atomic orbitals are distructive.

Ex: Hydrogen molecule:

The sum: ψ+H2 =ψ1s +ψ1s

This bonding orbital (called 1sσ, as it is produced from two s atomic orbitals)
is a simple symmetrical ellipsoid. It does not change sign upon inversion about the
centre of symmetry, which is marked by the subscript g (gerade = even). The orbital is
thus known as 1sσg.

The difference: ψ-H2 =ψ1s −ψ1s

In this antibonding orbital (called

1sσ∗) the charge is concentrated outside
the nuclei, which repel one another. This
orbital does change sign upon inversion,
which is marked by the subscript u
(ungerade = odd). It is thus known as 1sσu*.
formation of σg and σu* orbitals from two
atomic 2pz orbitals

formation of πg and πu* orbitals

from two atomic 2py orbitals
 A. Transitions involving electrons π, σ and n
σ → σ* transitions
The energy of this transitions is big. The corresponding maxima does not
appear in specific UV-Vis spectra (200 - 700 nm). (UV absorption!)

Ex: CH4 (only C-H bond) allows only σ → σ* transition.

The maximul of absorption is at 125 nm.

n → σ* transitions
Saturated compounds containing atoms with unpaired electrons (nonbonding
electrons) allows n → σ * transitions . The energy necessary for those transitions is
less than the energy needed for σ → σ * transitions. Transitions may be initiated by
radiation in the wavelength 150-250 nm.
The number of organic functional groups which have the maximum of absorption
in UV region is small.
n → π* and π → π* transitions

Most absorption bands of organic compounds are due to electronic transitions from
fundamental levels n or π on the excited levels π *. Absorption bands for these
transitions fall in the 200 nm - 700 nm region. These transitions require the presence, in
the molecule, of an unsaturated group which has π electrons.

n → π* transitions have low molar absorptivity (ε ~ 10 - 100 L/mol·cm).

π → π* transitions have high molar absorptivity (ε ~ 1.000 - 10.000 L/mol·cm).

The solvent could influence the positions of absorption bands.

With increasing polarity n → π * transitions are shifted to lower wavelengths (blue

shift). This shift is due to unpaired electrons (orbital energy decreases n)

With increasing polarity π → π * transitions are often (not always) shifted to higher
wavelengths (red shift). This is caused by attractive polarization forces between the
solvent and absorbent, which determine the decreas of ground and excited states
energy. This decrease is greater for excited state than for fundamental state, so the
difference in energy between the two levels decreases, resulting in a shift of the
absorption band to higher wave numbers (red shift).

This effect also influences n → π * transitions but is covered by the blue shift
due to unpaired electrons.
The wavelength of light absorbed is that having the energy required to
move an electron from a lower energy level to a higher energy level.
Transitions involving π and n orbitals (n = non-bonding) are important because they
can be used to identify conjugate systems, which have strong absorption.

The lowest energy transition is that between the HOMO (Highest occupied molecular
orbital) and LUMO (Lowest unoccupied molecular orbital) orbitals.

The absorption of electromagnetic radiation extract an electron from the HOMO and
transfer it on the LUMO, creating an excited state.

If the system is conjugated, the gap between HOMO and LUMO became lower, so
the frequency of radiation absorbed is smaller (the wavelength of radiation absorbed
is greater).

The color we see in ink, dyes, flowers, etc. is due to conjugation of organic molecules.
 Wavelengths below 200 nm are absorbed by air therefore, can not be
registered with a ordinary UV-Vis spectrometer.

"Vacuum UV" all parts must be maintained in a vacuum.

The vacuum UV absorption are caused by σ → σ * transitions.

These transitions correspond to simple bonds and are common to all molecules.

π -> π* transitions depend on

the conjugation, so it can reach
the visible region of radiation,
causing the color of substances.
B. Charge-transfer transitions

These electronic transitions usually appear in light absorption of inorganic

molecules.

For a molecule to allow a charge-transfer transition must have a component

(atom, group) able to donate an electron and another component must be able to
accept an electron.
The absorption of radiation involves an electron transfer from an orbital of a
donor to an orbital associated with an acceptor.

Charge-transfer transitions have high molar absorptivity (ε > 10.000 l/mol·cm).

Charge transfer transitions are common in metal-ligand complexes.

→ Typical metal-ligand transition: an electron from an orbital of the metal is transferred

to a π * orbital of the ligand.

→ If the metal has an empty d orbital, it is possible a transfer from ligand to metal.
 C. d-d transitions

d-d transitions correspond to the transition of an electron from a metal d orbital to

another metal d orbital.

Problem: → d orbitals have the symmetry g (even)

→ d-d transition is forbidden "symmetry forbidden".

Vibronic coupling: some vibration can remove the center of symmetry of the molecule.
d-d transitions are "weakly allowed”.

The intensity of d-d transitions is very low, because d-d transitions are forbidden.
Molar absorptivity is under 100 L/mol·cm.

type of transition Molar absorptivity ε

(L/mol·cm)
π-π* thousands
σ- σ* hundred - thousands
d-d 10-100
charge transfer >10.000
The color of a substance is the
transmitted color not the
absorbed color (the color that
remains after subtracting from
the incident light the absorbed
light).
 Conjugated molecules are those in which there is an alternation of single and
double bonds along a chain of carbon atoms.

The effect of bond conjugation is to shift the n→π* absorption to lower energies.

When two isolated double bonds are brought into conjugation, both levels are shifted
to give bonding and anti-bonding orbitals.

Vacuum UV or Far UV (λ < 190 nm )

UV/VIS
 The effect of conjugation is that the LUMO π* orbital is shifted downwards,
and the n→π* absorption shifts to lower energy (longer wavelengths).

Repeated conjugation increases this effect.

Absorption by a C=C double bond excites a π electron into an antibonding

π* orbital. The chromophore activity is due to an π → π* transition, corresponding to
absorption at 180 nm.
When the double bond is part of a conjugated chain, the energies of the
molecular orbitals lie closer together, and the π → π* transition moves to longer
wavelengths (lower energy). It may even lie in the visible region if the conjugated
system is long enough.
 An important example is the photochemical mechanism of vision.
The retina of the eye contains “visual purple”, a combination of a protein
with 11-cis-retinal, which acts as a chromophore and is a receptor of photons
entering the eye.
11-cis-retinal itself absorbs at 380 nm, but in combination with the protein
the absorption maximum shifts to ca. 500 nm and tails into the blue.
The conjugated double bonds are responsible for the ability of the
molecule to absorb over the entire visible region. They play another important role:
in its electronically excited state the conjugated chain can isomerize by twisting
about an excited C=C bond, forming 11-trans-retinal.

The primary step in

vision is photon
absorption followed by
isomerization, which
triggers a nerve impulse
to the brain.
Chromophores have well know absorption maxima:

Chromophore Example Excitation λmax, nm ε Solvent

C=C Ethene π __ > π* 171 15,000 hexane

C≡C 1-Hexyne π __ > π* 180 10,000 hexane
n __ > π* 290 15 hexane
C=O Ethanal
π __ > π* 180 10,000 hexane
n __ > π* 275 17 ethanol
N=O Nitromethane
π __ > π* 200 5,000 ethanol

C-X
Methyl bromide n __ > σ* 205 200 hexane
X=Br
Methyl Iodide n __ > σ* 255 360 hexane
X=I
The color of conjugated systems

The conjugation of double or triple bonds lead to increased absorptivity and determine
the shift of λmax to higher wavelengths (bathochromic shift):

The word "conjugation" is derived from a Latin word that means "to link together". In organic
chemistry, it is used to describe the situation that occurs when π systems are "linked together".

An "isolated" π system exists only between a single pair of adjacent atoms (e.g. C=C)
An "extended" π system exists over a longer series of atoms (e.g. C=C-C=C or C=C-C=O etc.).
An extended π system results in a extension of the chemical reactitvity.

A conjugated system requires that there is a continuous array of "π" orbitals that can
align to produce a bonding overlap along the whole system.
If a position in the chain does not provide a "π" orbital or if geometry prevents the
correct alignment, then the conjugation is broken at that point.
The result of conjugation is that there are extra π bonding interactions between the
adjacent π systems that results in an overall stabilisation of the system.
Conjugation = most efficient means of bringing about a bathochromic and
hyperchromic shift of an unsaturated chromophore:

max (nm) 
H2C
175 15,000
CH2

217 21,000

258 35,000

465 125,000

-carotene

O
n  p* 280 12
p  p* 189 900

O n  p* 280 27
p  p* 213 7,100
 Shape of UV-VIS Bands
The vibrational fine structure disappear for solutions but can be observed for gases.

I Gas phase, room temperature

II In isopentane-methylcyclohexane matrix, 77K

III In cyclohexane, room temperature ex. 1,2,4,5-tetrazine

IV In water, room temperature
Selection rules:
1. Spin rule: Changes in spin multiplicity are forbidden
Therefore, transitions between states with different multiplicity are forbidden
allowed transitions: singlet  singlet or triplet  triplet
forbidden transitions: singlet  triplet or triplet  singlet

Always there is a weak interaction between different

wave functions due to the multiplicity spin-orbit
coupling. Therefore the wave function corresponding to
the singlet state containing a small fraction of the triplet
wave function and vice versa.
This leads to the occurrence of singlet-triplet transitions
(intersystem crossing) with very low absorption
coefficient, but still noticeable.
2. Laporte rule: In an electronic transition there must be a change in the
parity (symmetry)

Therefore, a transition may be forbidden for symmetry reasons.

Electric dipole transition can occur only between states of opposite parity.

allowed transitions: g  u or u  g
forbidden transitions: g  g or u  u

g (gerade = even), u (ungerade = odd)

A symmetry forbidden transition may be observed due to vibronic

coupling (result in a far from perfect symmetry).

Molar absorptivity is very small and the corresponding absorption

bands have well-defined vibronic bands

Example: n → π * transitions of most solvents that can not form

hydrogen bonds. (ε ~ 100–1000 L/mol∙cm)