UNIT-4: UV Spectroscopy

Energy levels-Molecular orbitals-Theory of UV (electronic) spectra-Franck Condon

Principle -transition Probability, measurement of spectrum – Types of transition in Organic
molecules -Types of absorption bands – transition in metal complexes – Selection rules
Chromophore concept – Applications of UV Spectroscopy.

Introduction
UV-visible spectroscopy is a branch of spectroscopy in which transition occur due to
the excitation of electrons from one energy level to higher one by the interaction of
molecules with ultraviolet and visible lights. Absorption of photon results in electronic
transition of a molecule, and electrons are promoted from ground state to higher electronic
states. UV-visible spectroscopy involves an electron excitation phenomenon, so, also called
as Electronic Spectroscopy.

Energy levels
In an atom, an electron can revolve round the nucleus only in those allowed or
permissible orbits for which the angular momentum of the electron is an integral multiple of
h/2π. Here, h is the Planck’s constant = 6.64 × 10–34 Js. These orbits are called stationary
orbits and an electron revolving in these orbits does not radiate energy. An electron in each
stationary orbit possesses certain amount of energy and the stationary orbits are called as
energy levels. The energy levels are occupied by the electrons based on certain rules.

The Aufbau principle (from the German Aufbau, "building up, construction") was an
important part of Bohr's original concept of electron configuration. It may be stated as:
a maximum of two electrons are put into orbitals in the order of increasing orbital energy:
the lowest-energy orbitals are filled before electrons are placed in higher-energy orbitals.

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Pauli exclusion principle
An orbital can hold 0, 1, or 2 electrons only, and if there are two electrons in the
orbital, they must have opposite (paired) spins. Therefore, no two electrons in the same
atom can have the same set of four quantum numbers.

Hund’s Rule
Hund’s Rule states that orbitals of equal energy are each occupied by one electron
before any orbital is occupied by a second electron, and all electrons in singly occupied
orbitals must have the same spin.

Each electron in an atom is described by four different quantum numbers. The first three
(n, l, ml) specify the particular orbital of interest, and the fourth (ms) specifies how many
electrons can occupy that orbital.
1. Principal Quantum number (n)
n = 1, 2, 3… ∞ specifies the energy of an electron and the size of the orbital. All
orbitals that have the same value of n are said to be in the same shell (level). For a hydrogen
atom with n=1, the electron is in its ground state; if the electron is in the n = 2 orbital, it is
in an excited state. The total number of orbitals for a given n value is n2.
2. Angular momentum (Secondary, Azimunthal) Quantum number (l)
l = 0, ..., n-1 specifies the shape of an orbital with a particular principal quantum
number. The secondary quantum number divides the shells into smaller groups of orbitals
called subshells (sublevels). Usually, a letter code is used to identify l to avoid confusion
with n:
l 0 1 2 3 4 5 ...
Letter s p d f g h ...
The subshell with n = 2 and l=1 is the 2p subshell; if n = 3 and l = 0, it is the 3s subshell,
and so on. The value of l also has a slight effect on the energy of the subshell; the energy of
the subshell increases with l (s < p < d < f).
3. Magnetic Quantum number (ml)
ml = -l,..., 0, ..., +l specifies the orientation in space of an orbital of a given energy
(n) and shape (l). This number divides the subshell into individual orbitals which hold the

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electrons; there are 2l+1 orbitals in each subshell. Thus the s subshell has only one orbital,
the p subshell has three orbitals, and so on.

4. Spin Quantum number (ms)

ms = +½ or -½ specifies the orientation of the spin axis of an electron. An electron
can spin in only one of two directions (sometimes called up and down).
The Pauli exclusion principle (Wolfgang Pauli, Nobel Prize 1945) states that no two
electrons in the same atom can have identical values for all four of their quantum numbers.
What this means is that no more than two electrons can occupy the same orbital, and that
two electrons in the same orbital must have opposite spins.
Because an electron spins, it creates a magnetic field, which can be oriented in one of
two directions. For two electrons in the same orbital, the spins must be opposite to each
other; the spins are said to be paired. These substances are not attracted to magnets and are
said to be diamagnetic. Atoms with more electrons that spin in one direction than another
contain unpaired electrons. These substances are weakly attracted to magnets and are said
to be paramagnetic.

Table of Allowed Quantum Numbers

Number of Orbital Number of
N l ml
orbitals name electrons
1 0 0 1 1s 2
0 0 1 2s 2
2
1 -1, 0, +1 3 2p 6
0 0 1 3s 2
3 1 -1, 0, +1 3 3p 6
2 -2, -1, 0, +1, +2 5 3d 10
0 0 1 4s 2
1 -1, 0, +1 3 4p 6
4
2 -2, -1, 0, +1, +2 5 4d 10
3 -3, -2, -1, 0, +1, +2, +3 7 4f 14

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Writing electron configurations
The distribution of electrons among the orbitals of an atom is called the electron
configuration. The electrons are filled in according to a scheme known as the Aufbau
principle ("building-up"), which corresponds (for the most part) to increasing energy of the
subshells: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d and 7f.
Atomic orbitals are mathematical functions that describe the wave nature of
electrons (or electron pairs) in an atom. There are four different kinds of orbitals, denoted s,
p, d and f each with a different shape. To completely describe an electron in an atom, four
quantum numbers are needed: energy (n), angular momentum (ℓ), magnetic moment (mℓ),
and spin (ms).
Considering the wave function it is seen that the corresponding orbital must be
spherical, for at any distance from the nucleus. The spherical orbitals associated with the
value of l = 0 is called as s orbitals. The s orbitals are labeled according to their n quantum
numbers 1s, 2s, ……..ns. Orbitals with l=1 have twin-lobed shape. As n increases the shape
also increases in size. Such orbitals are labeled as p orbitals. For a given value of n there are
three p orbitals labeled as npx, npy, and npz.. These three is connected with three values of
m, i.e., m= +1, 0 and -1.
For l = 2 the n is ≥ 3. The m values are m = ± 2, ±1 or 0. The corresponding orbitals
are called as d orbitals. For l = 3 the n is ≥ 4. The m values are m = ±3, ± 2, ±1 or 0. The
corresponding orbitals are called as f orbitals. Orbitals with higher values of l are less
important. l=4 is labeled as g orbital and l = 5 is labeled as h orbital.
Molecular orbital
A molecular orbital (MO) is a mathematical function that describes the wave-like
behavior of an electron in a molecule. This function can be used to calculate chemical and
physical properties such as the probability of finding an electron in any specific region.
Molecular orbital (MO) description of homonuclear diatomic molecules
Atomic orbitals having similar energy will combine to form the MO. The simplest
way to form molecular orbital is to combine the corresponding orbitals on two atoms (i.e. 1s
+ 1s, 2s + 2s, etc.). The appropriate combinations are
σ(1s) = 1sA + 1sB σ(1s)* = 1sA - 1sB
σ(2s) = 2sA + 2sB σ(2s)* = 2sA - 2sB

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 σ(2p) = 2pxA + 2pxB σ(2p)* = 2pxA - 2pxB
∏(2py) = 2pyA + 2pyB ∏(2pz) = 2pzA + 2pzB ∏(2py)* = 2pyA - 2pyB
The 1s orbitals from two different atoms will form σ g(1s)* and σu(1s)* just like the
MO’s of hydrogen molecule. In the similar way 2s orbitals from two different atoms will
form σg(2s)* and σu(1s)* MO. These two molecular orbitals will look like σg(2s) and
σu(2s)* . Since an atomic 2s orbital has higher energy than atomic 1s orbital σg(2s) and
σu(2s)* MO will have higher energy in comparison to σg(1s) and σu(1s)* MO respectively.
So the ordering of the molecular orbitals discussed so far will be
σg(1s) < σu(1s)* < σg(2s) < σu(2s)* .

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Combination of the 2p orbitals
Except hydrogen atom 2p orbital energy is higher than the 2s orbital energy; the
bonding and antibonding molecular orbital formed from the combination of 2p orbital will
have higher energy than σg(2s) and σu(2s)* respectively. If we consider the x axis as
molecular axis then these two orbitals will be denoted as σg(2p) and σu(2p)*.The remaining
2p orbitals i.e. 2py, and 2pz will form П molecular orbitals by lateral overlapping. The
bonding and antibonding molecular orbital forming by overlapping 2py orbitals are denoted
Пu(2py) and Пg(2py)* . These two orbital will be directed towards Y axis. The 2p z combined
in the similar manner will result in bonding and antibonding П MO but these will be
directed along the Z axis. The bonding П orbitals arising from the combination of two 2p y
atomic orbitals and two 2pz will degenerate and similarly the antibonding П* MOs.
As the atomic number increases from lithium to fluorine, the energy of the σg(2p)
and energy of Пu(2py) and Пu(2pz) orbitals approaches to each other and interchange order
in going from N2 and O2 . But in case of N2 molecule the MO diagram, the energy of the
σg(2p) orbital will be less than that of Пu(2py) and Пu(2pz) orbitals.
Bond order
The net bonding in a diatomic molecule is defined by a quantity called bond order, b;
b = (n-n*)/2
Where n is the number of electron in the bonding orbital and n* is the number of electrons
in the antibonding orbital. Bond order correlates with bond length and bond strength. If the
bond order between atoms of a given pair of elements is higher, then the bond length will be
shorter and consequently the bond will be stronger. The bond strength is measured by bond
dissociation energy which is the energy required to separate the atoms to infinity. Single
bonds have bond order one; double bonds have two; and so on. The bond order zero
indicates that t here is no bond between the given pair of atoms. For example bond order for
He2 is zero, because there are two electrons in both
bonding and antibonding orbital. For this reason He2 molecule does not exist. Bond order of
H2 gas molecule is 1. Bond order of N2- is 3 (N≡N).
Molecular orbital theory of heteronuclear diatomic molecules
Different types of atoms have different capacities to attract the electrons. The
bonding electron will be more stable in the presence of the nuclei of the atom having greater

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electronegativity, i.e. the atom having lower energy. Probability of finding the bonded
electrons will be more near that nucleus. The electron cloud will be distorted towards
that nucleus and hence the MO will resemble that AO more than the AO on the less
electronegative atom.

Because there are no unpaired electrons, H2 is diamagnetic.

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4.

HOMO and LUMO

The highest occupied molecular orbital and lowest unoccupied molecular orbital are often
referred to as the HOMO and LUMO, respectively. The difference of the energies of the HOMO
and LUMO, termed the band gap, can sometimes serve as a measure of the excitability of the
molecule: the smaller the energy, the more easily it will be excited.

Electronic spectroscopy
The energies involved when molecules make transitions by changing their electronic
distributions are of the order of several electron volts and so the photons emitted or
absorbed lie in the visible and ultraviolet regions of the electromagnetic spectrum.
Electronic spectra give information about the electronic structures of molecules, and by
analyzing them we are able to deduce the energies of electrons in different molecular
orbitals and therefore to test the theories of molecular structure.
Changes in electronic energy involve relatively large quanta, so there are
simultaneous changes in the vibrational and rotational changes of the molecule. The
electron in a molecule can be excited from an occupied molecular orbital to an empty or

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partially filled molecular orbital. This is known as electronic transition. The radiation
required for the electronic transition lies in the visible or ultraviolet region. A molecule in
each stable electronic level can execute vibrational and rotational motions. The total energy
of the molecule is given as : Etotal  Ee  Ev  Er
The electronic transitions are accompanied by changes in vibrational and rotational
energy levels. The vibrational transitions appear as the coarse structure where as
rotational transition as the fine structure. The electronic spectra of molecules are

found in the wavelength range 1000-8000 Å.

Electronic spectra of diatomic molecules

The pure rotational spectra are shown only by molecules possessing a permanent

electric dipole moment, and vibrational spectra require a change of dipole moment

during motion, electronic spectra are given by all molecules since changes in the

electron distribution in a molecule are always accompanied by a dipole change. It

means that homonuclear molecules (e.g. H2, N2 etc.) which show no rotational or

vibration rotational spectra, do give an electronic spectrum and show a vibrational

and rotational structure in their spectra from which rotational constants (B) and

bond vibration frequencies ( e ) may be derived.

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The diagram shows that the lines in a band crowd together more closely at higher
frequencies; this is direct consequences of anharmonicity of the upper state vibration which
causes the excited vibrational levels to converge. An analytical expression can easily be
written for this spectrum.

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Franck Condon Principle
The vibrational lines in a progression are not all observed to be of the same intensity.
In some spectra the (0, 0) transition is the strongest, in others intensity increases to a
maximum at some value of v´, while in yet others only a few vibrational lines with high v´
are seen, followed by a continuum. All these types of spectrum are readily explained in
terms of the Franck Condon Principle. It states that an electronic transition takes place
so rapidly that a vibrating molecule does not change its internuclear distance
appreciably during the transition.
Franck-Condon principle also states that transitions from one state to another are
most probable when nuclei are in their mean positions i.e., observed transitions between
two states should start from extreme positions of vibrational level. The variation of energy
of a diatomic molecule with internuclear distance is shown by Morse curve, which
represents the energy when one atom is considered, fixed on the r = 0 axis and the other is
allowed to oscillate between limits of the curve. For v = 0, 1, 3 ... the most probable
positions steadily approach the extremities until for high v, the quantum and classical
picture merge. This behaviour is shown in Fig. 2, where we plot the probability distribution
in each vibrational state against internuclear distances. Fig. 2 shows the variation of
vibrational probability function 2 with internuclear distance, r where  is the vibrational
wave function.

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The probability of a molecule being at a particular internuclear distance is a function of the
distance as shown in Fig. 2. The electronic transition probability is given by the equation,
(µx – dipole moment component and am(t) – transition amplitude)

Polyatomic molecules
All organic compounds are capable of absorbing electromagnetic radiation

because all contain valence electrons that can be excited to higher energy levels.

The excitation energies associated with electrons forming most single bonds are

high.

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 The energies for the various types of molecular orbitals differ significantly as shown
in the figure given below.

It is known that ultraviolet energy is quantized. Hence the absorption spectrum

arising from a single electronic transition should consist of a single discrete or
discontinuous line. A discrete line is not obtained because electronic absorption is
superimposed on rotational and vibrational levels. It has been observed that spectra of
simple molecules in the gaseous state consists of narrow absorption peaks, each
representing a transition from a particular combination of vibrational and rotational levels in
the electronic ground state to the corresponding combination in excited state. It is shown in
the following figure where vibrational levels are designated as v0, v1, v2, v3 ---.
At ordinary temperature, most of the molecules in the electronic ground state are
expected to be in zero vibrational level (Gv0). As a result there will be many electronic
transitions from this level. In molecules containing more atoms, the multiplicity of the
vibrational sublevels and closeness of their spacings cause the discrete bands to coalesce
and hence broad absorption bonds are obtained. Generally, energy level of non bonding
electron lies in between those of the bonding and the antibonding orbitals. Electronic
transitions among certain of the energy levels can be brought about by the absorption of
radiation.

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The promotion of an electron e.g. from a - bonding orbital to an antibonding * orbital is
designated as *. The n * transition requires less energy compared * or  
 * transition. As n-electrons do not form bonds, there are no antibonding orbitals
associated with them. There are four important types of transition :
(a)    * (b) n  * (c)    * (d) n  *
The energies required for various transitions are in the order:

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Selection rules

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Chromophore and Auxochrome

Red shift or Bathochromic shift :

It is shift of absorption maximum (max) towards shorter wavelength. It may be

produced by a change of medium or by presence of an auxochrome. The bathchromic
groups, like primary, secondary or tertiary amino groups, increase the colour.
Blue shift or Hypsochromic shift
It is shift of absorption maximum (max) towards shorter wavelength. This may be
caused by a change of medium and also by such phenomenon as the removal of
conjugation. For example, the conjugation of lone pair of electrons on the nitrogen atom of
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aniline with the -bond system of benzene ring is removed on protonation. Aniline absorbs
at 230 nm (, 8,600) but in acid solution the main peak is almost identical with that of
benzene being new at 203 nm (, 7500). A blue shift has occurred.

Electronic spectra of transition metal complexes

The ions and complexes of the 18 elements in first two transition series are coloured
(with very few exception) in at least one oxidation state. The aqueous Cu (II) ion is pale
blue in colour but dark blue in colour when it is complexed with ammonia.
The colour of the transition metal complexes is mainly attributed to d-d transition. Metals of
the first two transition series are characterized by having five partially filled d-orbitals (3d
in the first series and 4d in second series) and each is capable of accompanying a pair of
electrons. Electrons in these orbital generally do not take part in bond formation. The
spectra characteristics of transition metals arise from electronic transitions that involve the
various energy levels of these d-orbitals.
Crystal field theory and Molecular orbital theory are the two important theories
proposed to explain the colour of the transition metal ions and influence of the environment
on these colours. Both these theories are based on the fact that the energies of d-orbitals of
the transition metal ions in solution are not identical and that the absorption involves the
transition of electron, from d-orbital of lower energy to one of higher energy.
The energies of the five d-orbitals are, however identical in dilute gaseous state
because of the absence of an external electrical and magnetic field. In case of solution,
complex formation occurs between the metal ion and water or same other ligand (Lewis
base). Splitting of the energies of the d-orbitals occurs because of differential electrostatic
forces of repulsion taking place between the electron pair of the donor and the electron in
the various d-orbitals of the central metal ion. It should be noted that out of five d-orbitals
(dx2-y2, dz2, dxy, dyz, and dxz) the three orbitals dxy, dyz & dxz are similar in all respects except
for their special orientation. These three orbitals occupy spaces between the three axes.
Hence they have minimum electron densities along the axes and maximum densities on the
diagonal between the axes.

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The electron density of dx2-y2 and dz2 orbital is directed along the axes. Suppose a
transition metal ion is coordinated to six molecules of water as ligand (Lewis base). These
groups may be regarded as being evenly distributed around the central metal ion, one ligand
being located at each end of the three axes as shown in figure given below. The resulting
transition metal complex has octahedral structure, which is the most common orientation. In
this arrangement negative ends of the water dipoles are pointed towards the metal ion.

Tetrahedral configuration (in which the four groups are symmetrically distributed
around the metal ion) and square planar configuration (in which four ligands and the metal
ion lie in a single plane) have been encountered. The magnitude of  depends upon valency
state of the metal ion, position of the element in P.T. and a number of other factors. The

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ligand field strength is a measure of the extent to which is a complexing group will split the
energies of d-electrons. Hence a complexing agent with high ligand field strength is
expected to cause  to be large. Some ligands in order of increasing ligand field strengths
are I– < Br – < SCN– < Cl – < OH– < H2N < NH3 < H2N-CH2-CH2-NH2 < NO2– < CN-.
This order of ligand field strength applied almost to all transition metal ions and allows
qualitative prediction as to the relative position of absorption peaks for the various
complexes of a given transition metal ion. Since  increases with increase in field strength,
the wavelength of absorption maximum (max) decreases.

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UV-visible spectroscopy
Introduction
Ultraviolet and visible spectroscopy deals with the recording of the absorption of
radiations in the ultraviolet and visible regions of the electromagnetic spectrum. The
ultraviolet region extends from 10 to 400 nm. It is subdivided into the near ultraviolet
(quartz) region (200-400 nm) and the far or vacuum ultraviolet region (10-200 nm). The
visible region extends from 400 to 800 nm. The absorption of electromagnetic radiations in
the UV and visible regions induces the excitation of an electron from a lower to higher
molecular orbital (electronic energy level). UV and visible spectroscopy is mainly used for
detecting the presence and elucidating the nature of the conjugated multiple bonds or
aromatic ring.
Absorption Laws and Molar Absorptivity
A UV-visible spectrophotometer records a UV or visible spectrum (Fig. 5) as a plot
of wavelengths of absorbed radiations versus the intensity of absorption in terms of
absorbance (optical density) A or molar absorptivity (molar extinction coefficient) ε as
defined by the Lambert-Beer law. According to Lambert's law, the fraction of incident
monochromatic radiation absorbed by a homogeneous medium is independent of the
intensity of the incident radiation while Beer's law states that the absorption of a
monochromatic radiation by a homogeneous medium is proportional to the number of
absorbing molecules. From these laws, the remaining variables give the following equation
which expresses the Lambert-Beer law.

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Transition Probability: Allowed and Forbidden Transitions
On exposure to UV or visible radiation, a molecule may or may not absorb the
radiation, i.e. it may or may not undergo electronic excitation. The molar absorptivity at
maximum absorption 𝜺𝒎𝒂𝒙 = 𝑷 𝒂 × 𝟎. 𝟖𝟕 × 𝟏𝟎𝟐𝟎
where P is the transition probability with values from 0 to 1 and a the target area of the
absorbing system, i.e. a chromophore. A chromophore with a length of the order of 10 Å or
10-7 cm and with unit probability will have εmax value of ~ 105. Thus, there is a direct
relationship between the area of a chromophore and its absorption intensity (εmax).
Transitions with εmax values > 104 are called allowed transitions and are generally caused by
π to π* transitions, e.g. in 1, 3-butadiene, the absorption at 217 nm, εmax = 21000 results
from the allowed transition. Transitions with εmax values < 104 are called forbidden
transitions. These are generally caused by n to π* transitions, e.g. in carbonyl compounds,
the absorption near 300 nm with εmax values of 10-100 results from the forbidden
transition.

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Instrumentation
Instruments for measuring the absorption of U.V. or visible radiation are made up of the
following components,
1. Sources (UV and visible) 2. Filter or monochromator
3. Sample containers or sample cells 4. Detector

1. Various UV radiation sources are,

a. Deuterium lamp b. Hydrogen lamp c. Tungsten lamp
d. Xenon discharge lamp e. Mercury arc lamp
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Various Visible radiation sources are,
a. Tungsten lamp b. Mercury vapour lamp c. Carbon arc lamp
2. Filters or monochromators
All monochromators contain the following component parts;
a) An entrance slit b) A collimating lens c) A dispersing device (a prism or
a grating) d) A focusing lens e) An exit slit
Polychromatic radiation (radiation of more than one wavelength) enters the monochromator
through the entrance slit. The beam is collimated, and then strikes the dispersing element at
an angle. The beam is split into its component wavelengths by the grating or prism. By
moving the dispersing element or the exit slit, radiation of only a particular wavelength
leaves the monochromator through the exit slit.
3. Sample containers or sample cells
A variety of sample cells available for UV region. The choice of sample cell is based on
a) the path length, shape, size b) the transmission characteristics at the desired
wavelength c) the relative expense
The cell holding the sample should be transparent to the wavelength region to be recorded.
Quartz or fused silica cuvettes are required for spectroscopy in the UV region. Silicate
glasses can be used for the manufacture of cuvettes for use between 350 and 2000 nm. The
thickness of the cell is generally 1 cm. cells may be rectangular in shape or cylindrical with
flat ends.
4. Detectors
In order to detect radiation, three types of photosensitive devices are,
a. photovoltaic cells or barrier- layer cell b. phototubes or photoemissive tubes
c. photomultiplier tubes.

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The following figure shows the UV-visible spectrum of acetone.

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Applications
1. Detection of Impurities
 It is one of the best methods for determination of impurities in organic

molecules.
 Additional peaks can be observed due to impurities in the sample and it can be

compared with that of standard raw material.

 By also measuring the absorbance at specific wavelength, the impurities can be

detected.
2. Structure elucidation of organic compounds
 It is useful in the structure elucidation of organic molecules, such as in detecting

the presence or absence of unsaturation, the presence of hetero atoms.

3. UV absorption spectroscopy can be used for the quantitative determination of compounds
that absorb UV radiation.
4. UV absorption spectroscopy can characterize those types of compounds which absorbs
UV radiation thus used in qualitative determination of compounds. Identification is done by
comparing the absorption spectrum with the spectra of known compounds.
5. This technique is used to detect the presence or absence of functional group in the
compound. Absence of a band at particular wavelength regarded as an evidence for absence
of particular group.
6. Kinetics of reaction can also be studied using UV spectroscopy. The UV radiation is
passed through the reaction cell and the absorbance changes can be observed.
7. Many drugs are either in the form of raw material or in the form of formulation. They can
be assayed by making a suitable solution of the drug in a solvent and measuring the
absorbance at specific wavelength.
8. Molecular weights of compounds can be measured spectrophotometrically by preparing
the suitable derivatives of these compounds.
9. UV spectrophotometer may be used as a detector for HPLC.

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