Study Material/chap.2 Structure and Bonding: Kiita9

KIITA9
Study material/Chap.2
Structure and Bonding
Mentor: DR. Indrajit Chakraborty
10/29/2010
Classical Mechanics (Newtonian Mechanics)
The branch of science based on Newton’s laws of motion & Maxwell’s electromagnetic wave-
theory to explain the phenomenon related to motion and energy. According to classical mechanics, it
should be possible to determine simultaneously the position and velocity of a moving particle. Classical
mechanics assumes that energy is emitted or absorbed in a continuous manner.
Classical mechanics fails to provide satisfactory explanation for the following phenomena:
i. Black Body Radiation
ii. Photoelectric Effect
iii. Atomic and molecular spectra
iv. Heat capacities of solids
Black Body Spectrum: Failure of Classical Mechanics

Black-Body Radation Laws
1- The Wien‘s Law (Displacement & Distribution)
2- The Stefan-Boltzmann Law
3- The Rayleigh-Jeans Law
4- The Planck Law
A black body is an ideal body which allows the whole of the incident radiation to pass into itself (
without reflecting the energy ) and absorbs within itself this whole incident radiation (without passing
on the energy). This propety is valid for radiation corresponding to all wavelengths and to all angels of
incidence. Therefore, the black body is an ideal absorber of incident radaition.
Blackbodies absorb and incandescently re-emit radiation in a characteristic, continuous spectrum. A
Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

black body is not only a perfect absorber of the radiant energy, but also a perfect radiator. The black
body radiation emitted usually consists of infra-red, light and ultra violet which all produce a heating
effect.
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The energy distribution, or energy spectral density or intensity () is the energy per unit volume of the
cavity that is emitted in the wavelength interval λ to λ + dλ. Note the total area under the curve
increases as the temperature increases, indicating that the hotter an object is, and the more energy it
radiates per unit volume.
The graph shows:

a. The black body radiation curves have the same nature, irrespective of the size, shape or
material of the black body.
b. For each temperature there is a wavelength (max) at which the intensity of the radiation is
maximum.
c. Higher the temperature, more pronounced is the maximum.
d. As the temperature increases, the peak wavelength emitted by the black body decreases.
It therefore begins to move from the infra-red towards the visible part of the spectrum
(Wien displacement law).
e. The area under the curve for a particular temperature gives the total energy emitted by
the black body per unit area per second for the complete spectrum.
f. As temperature increases, the total energy emitted increases, because the total area
under the curve increases (Stefan-Boltzmann law).
g. None of the graphs touch the x-axis so they emit at every wavelength. This means that
some visible radiation is emitted even at these lower temperatures and at any
temperature above absolute zero; a black body will emit some visible light.
h. It also shows that the relationship is not linear as the area does not increase in even steps.
Analysis of the data from black body emitters led to the formulation of the Wien displacement
law. This law states that the dominant wavelength at which a blackbody emits electromagnetic radiation
is inversely proportional to the Kelvin temperature of the object.
max = b/T

where,  max is the wavelength at which the energy radiated is maximum and ‘T’ is the temperature in
Kelvin. ‘b‘ is a constant of proportionality, called Wien's displacement constant and equals 2.897 768
5(51) × 10–3 m K = 2.897768 5(51) × 106 nm K. According to this law the peak wavelength emitted by the
black body decreases as temperature increases. This decrease in wavelength explains why objects glow
first red, then orange-red, then yellow, then even blue.
Wien distribution law is a law of physics that is used to describe the spectrum of thermal
radiation. The equation does accurately describe the short wavelength (high frequency) spectrum of
thermal emission from objects, but it fails to accurately fit the experimental data for long wavelengths
(low frequency) emission:
Wien’s Distribution law: =
Where E is the emmisisive power of the black body corresponding to the wavelength , c is velocity of
light, h is plank constant, k is Boltzman const. and T is the absolute temperature. However, this law
disagrees with experimental data at long wavelengths.
The Stefan-Boltzmann law states that a blackbody radiates electromagnetic waves with a total
energy flux ‘E’ directly proportional to the fourth power of the Kelvin temperature ‘T’ of the object:
E = T4
2
where,  = 5.67 x 10-8 J s-1 m-2 K-4, known as the Stefan-Boltzmann constant. According to this law as
temperature increases, the total energy emitted increases, because the total area under the curve
increases. Thus this law explains the growth in the height of the curve as the temperature increases.
Notice that this growth is very abrupt.
The Rayleigh–Jeans Law expresses the spectral intensity of a blackbody as a function of
temperature through classical arguments. According to Rayleigh–Jeans Law
8
=
That means at any particular temperature the spectral intensity should increase without bound as 0
i.e. But for black-body radiation the energy distribution plotted versus the wavelength exhibits a
maximum. This failure has become known as the ultraviolet catastrophe. However, at long
wavelengths, the match is good. The Rayleigh-Jeans Law predicted no peak wavelength.
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To obtain agreement between the theoretical and experimental curves, Planck derived an equation,
the Planck distribution, which fits the experimental curve at all wavelengths. According to Plank a black
body radiates or absorbs the energy such as light or heat not continuously but in whole number (1,2,3…)
of a small energy packet called quantum. The energy of each quantum, E = h, h is the Planck constant,
 is the frequency of the oscillator. A small quantized energy packet is called a photon. Oscillators are

excited only if they can acquire the amount of energy of at least h according to Planck’s quantum
theory.
According to Plank: =
At lower wavelength (higher frequency) T is small, ≫ 1, so at lower wavelength Plank’s

law becomes:
= ⇒ Wien’s law
At higher wavelength (lower frequency) T is large, = + 1, so at higher wavelength
Plank’s law becomes:
= = ⇒ Rayleigh–Jeans Law
Explanation of Blackbody radiation by quantum mechanics:

The spectrum of blackbody radiation (below) shows that some wavelengths get more energy than
others. Three spectra are shown, for three different temperatures.
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Classical physics said that each frequency of vibration should have the same energy. Since there
is no limit to how great the frequency can be, there is no limit to the energy of the vibrating electrons at
high frequencies. This means that, according to classical physics, there should be no limit to the energy
of the light produced by the electrons vibrating at high frequencies. WRONG!! Experimentally, the
blackbody spectrum always becomes small at the left-hand side (short wavelength, high frequency).
At about 1900, Max Planck came up with the solution. He proposed that the classical idea that
each frequency of vibration should have the same energy must be wrong. Instead, he said that energy is
not shared equally by electrons that vibrate with different frequencies. Planck said that energy comes in
clumps. He called a clump of energy a quantum. The size of a clump of energy --- a quantum --- depends
on the frequency of vibration. Here is Planck's rule for the a quantum of energy for a vibrating electron:
energy of a quantum = (a calibration constant) x (frequency of vibration)
or, E = h
where h, the calibration constant, is today called Planck's constant. Its value is about 6 x 10-34, very tiny!
So how does this explain the spectrum of blackbody radiation? Planck said that an electron vibrating
with a frequency f could only have an energy of 1 hf, 2 hf, 3 hf, 4 hf, ... ; that is,
energy of vibrating electron = (any integer) x h
But the electron has to have at least one quantum of energy if it is going to vibrate. If it doesn't

have at least energy of 1hf, it will not vibrate at all and can't produce any light. "A ha!" said Planck: at
high frequencies the amount of energy in a quantum, hf, is so large that the high-frequency vibrations
can never get going! This is why the blackbody spectrum always becomes small at the left-hand (high
frequency) side.
Photoelectric Effect
The photoelectric effect refers to the emission, or ejection, of electrons from the surface of,
generally, a metal in response to incident light. Energy contained within the incident light is absorbed by
electrons within the metal, giving the electrons sufficient energy to be 'knocked' out of, that is, emitted
from, the surface of the metal. Electrons emitted in this manner may be referred to as "photoelectrons".
The key experimental facts about the photoelectric effect are the following:
a) The emission of photoelectrons will not occur at all, if the frequency of the incident
electromagnetic radiation (light) is less than a certain frequency called the cutoff frequency or
threshold frequency. Below the cutoff frequency there would be no photoelectrons regardless
of the intensity of the incident light.
b) The maximum KE of the ejected photoelectrons depends on both the frequency of the incident
electromagnetic radiation and the metal itself.
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c) If the frequency of the incident radiation (light) is larger than the cutoff frequency, then the no.
of emitted photoelectrons is proportional to the intensity of the radiation.
Einstein proposed that this phenomenon could be explained by thinking of light as little packets of
energy, known as photons (particle character). The energy of one photon is quantized, E=hh= Plank
Constant,  = frequency of radiation.
Max. K.E. of an ejected electron= = h=frequency of the incident photon;
work function = hThreshold Frequency. Because the kinetic energy of the electron must be
positive, it follows that ˃ in order for the photoelectric effect to occur. This equation also supports
the fact (b) said above.
Significance of Photoelectric Effect

According to classical Maxwell wave theory of light the average energy carried by an ejected
(photoelectric) electron should be proportional to the intensity of the incident light. But, in reality this
argument totally fails for photoelectric effect. Rather it has been found that frequency of the incident
light plays a vital role in determining the KE of a photoelectron - only the particle character of light is
sufficient enough to explain this observation as explained by Einstein’s model. Moreover Einstein model
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also explains the other observation that increasing intensity would increase the no. of ejected electrons
with same average KE.
Thus, the photoelectric effect is perhaps the most direct and convincing evidence of the
existence of photons and the 'corpuscular' nature of light and electromagnetic radiation. That is, it
provides undeniable evidence of the quantization of the electromagnetic field and the limitations of the
classical field equations of Maxwell.
As the alkali metals have lowest values for the first ionization potential, these metals best
exhibit the photoelectric effect.
Line Spectrum: Another Proof Quantum Theory of Radiation
In addition to measuring the spectra of blackbody radiation in the 19th century, experimental
physicists also were familiar with the spectra emitted by gases through which an electrical discharge (an
electric current with enough energy to strip some of the electrons from the atoms of the gas) was
passing. Such spectra consist of emissions at discrete, separated wavelengths, rather than over a
continuous band of wavelengths as in blackbody spectra. These spectra are called line spectra because

of their appearance when they are viewed with a spectrometer.
Line spectra are another example of phenomena that could not be explained by classical physics.
In physics, atomic spectral lines are of two types:
 An emission line is formed when an electron makes a transition from higher energy stationary
orbit of an atom, to a lower one, emitting a photon of a particular energy and wavelength.
 An absorption line is formed when an electron makes a transition from a lower energy
stationary orbit of an atom, to a higher one, with a photon being absorbed in the process.
According to Bohr’s atomic structure model the electrons occupy discrete stable orbits without
radiating their energy. The discreteness was a result of the quantization of the orbits, with each orbit
corresponding to a specific quantized energy for the electron.
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The electron was required to have a certain minimum quantum of energy corresponding to a
smallest orbit; thus, the quantum rules did not permit the electron to fall into the nucleus. However, an
electron could jump from a higher orbit to a lower orbit and emit a photon in the process. The energy of
the photon could take on only the value corresponding to the difference between the energy of the
electron in the higher and lower orbits. An electron could also absorb a photon and jump from a lower
orbit to a higher orbit if the photon energy equaled the difference in orbit energies
That means an electron can move from one energy level to another either by emission or absorption
of one photon having quantized energy hν, where h is Planck's constant and is the frequency of
absorbed or emitted energy in form of a photon.
The two states must be bound states in which the electron is bound to the atom, so the transition is
sometimes referred to as a "bound–bound" transition, as opposed to a transition in which the electron
is ejected out of the atom completely ("bound–free" transition) into a continuum state, leaving an
ionized atom, and generating continuum radiation.
A photoncarries the energy equal to the energy difference (E) between the levels is released or
absorbed in the process. The frequency  at which the spectral line occurs is related to the photon
energy E by Planck's lawE = hν= E = E2-E1, whereh is Planck's constant. E2& E1 are the energies of two
bound states (stationary states) for electronic transition.
In case of H-atom (one electron system), E = hν= (E)n2→n1 = En2 – En1 = − ,
e, m, hand c are known.n2˃n1
E=ℎ = −
⇒ 1 (cm-1) = − = − , R=Rydberg Constant = 109,677cm-1
1/frequency of the line spectrum in cm-1.

Different types of Emission Spectral Lines for Hydrogen.
de-Broglie’s Equation
de-Broglie derived an equation between the magnitude of the wavelength associated with the
mass ‘m’ of a moving body and its velocity.
According to Plank, the photon energy is ‘E’ is given by the eqn. E=hh=plank const, n=
frequency of radiation.
Now applying Einstein’s mass-energy relationship, E=mc2, where c= velocity of radiation
∴mc2= hhc/
∴mc=h/
Momentum (p) = h/wavelength
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∴ Momentum∝ (1/wavelength)
The above equation is called de-Broglie’s Equation and the wavelength is called de-Broglie’s
Wavelength.
Distinction between a particle and a wave: The concept of a particle and a wave can be under-stood by
the different points of distinction between them given in the following table
Particle Wave
1. A wave is spread out in space e.g. on throwing a
1. A particle occupies a well-defined stone in a pond of water, the waves start moving out in
position in space i.e. a particle is localized in the form of concentric circles. Similarly, the sound of
space e.g. a grain of sand, a cricket ball etc. the speaker reaches everybody in the audience. Thus a
wave is delocalized in space.
2. When a particular space is occupied by
one particle, the same space cannot be
2. Two or more waves can coexist in the same region of
occupied simultaneously by any other
space and hence interfere.
particle. In other words, particles do not
interfere.
3. When a number of particles are present 3. When a number of waves are present in a given
in a given region of space, their total value region of space, due to interference, the resultant wave
is equal to their sum i.e. it is neither less nor can be larger or smaller than the individual waves i.e.
more. interference may be constructive or destructive.
Significance of de-Broglie Equation

i. The wave character of large objects (in motion), has no practical significance, since their
wavelength is too small to be observed and hence cannot be measured
ii. The wave character of small objects (in motion), has practical significance, since their
wavelength is easily observed in electromagnetic sdpectrum
Thus the significance of de Broglie equation lies in the fact that it relates the particle character
with the wave character of matter. Although the de Broglie equation is applicable to all material objects

but it has significance only in case of micro-scopic particles. This will be clear from the following
example:
Consider a ball of mass 0.1 kg moving with a speed of 60 m s-1. From de Broglie equation, the
. ×
wavelength of the associated wave is = . ×
or approx. 10-34 m. It is apparent that this
wavelength is too small for ordinary observation. On the other hand, an electron with a rest mass equal
to 9.11 × 10-31 kg i.e. approx. 10-30 kg moving at the same speed would have a wavelength =
. ×
≈ 10 m i.e. 105 Å which can be easily measured experimentally.
×
Since we come across macroscopic objects in our everyday life, therefore de Broglie relationship
has no significance in everyday life. That is why we do not observe any wave nature associated with the
motion of a running car or a cricket ball etc.
Justification of Dual Character

According to de-Broglie a moving electron will not only have the
particle character, but also wave property (). The quantum restriction of
Bohr’s theory for an electron in motion in the circular orbit is that the
angular momentum (mvr) is an integral multiple (n) of h/2
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mvr = nh/2
2r=nh/mv = nfrom de-Broglie’s Equation)
Now the electron wave of wavelength  can be accommodated in Bohr’s orbit only if the
circumference of the orbit, 2r, is an integral multiple of wavelength  (wave in phase). Thus de-
Broglie’s idea of standing electron waves stands justified. However, if the circumference is bigger, or
smaller than n , the wave train will go out of phase and the destructive interference of waves causes
radiation of energy.
In other words we can say that Bohr’s concept and de-Broglie’s concept agree with each other
when the electron-waves are in phase which is nothing but the confirmation of Bohr’s theory by de-
Broglie equation.
Derivation of Bohr’s postulate of angular momentum from de Broglie equation

According to Bohr’s model, the electron revolves around the nucleus in circular orbits. According
to de Broglie concept, the electron is not only a particle but has a wave character. Thus in order that the
wave may be completely in phase (Fig. (a), the circumference of the orbit must be equal to an integral
multiple of wavelength () i.e. 2r=nwhere r is the Bohr radius of the orbit, and n is an integer.
But = h/mv (from de-Broglie Equation), ‘v’ is the velocity of the electron in the Bohr orbit,
‘m’=mass of the electron
∴2r=nh/mv
⇒mvr = nh/2, which is Bohr’s postulate of angular momentum.

The Uncertainty Principle
The Uncertainty principle is an important consequence of the wave-particle duality of matter and
radiation and is inherent to the quantum description of nature. Simply stated, it is impossible to know
both the exact position and the exact momentum of an object simultaneously.
Uncertainty in position = x, Uncertainty in momentum = p
x.p ≥h/4

Significance of Heisenberg’s uncertainty principle
1. It is impossible to know both the position and momentum exactly, i.e., x=0 and p=0
2. These uncertainties are inherent in the physical world and have nothing to do with the skill
of the observer
3. Because ‘h’ is so small, these uncertainties are not observable in normal everyday situations
Heisenberg’s Uncertainty Principle is important for small particles:-

For a moving ball of iron weighing 500 g, the uncertainty becomes:
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x.mxv) ≥ h/4
or, x ×v ≥ h/4m
. ×
≥ ≈ 2.5 × 10-31erg sec-1 g
× ×
which is very small and negligible. Therefore for large objects the uncertainty measurement is practically
nil.
But for an electron of mass = 9.1 × 10-28 g, the uncertainty becomes:
x ×v ≥ h/4m
. ×
≥ ≈ 0.15 erg sec-1 g
× × . ×
this value is large enough in comparison with the size of the electron and thus in no way negligible.
Application of Heisenberg’s uncertainty principle:-

a) Electron cannot exist in the Nucleus
Proof: On the basis of Heisenberg’s uncertainty principle, it can be shown why electrons cannot
exist within the atomic nucleus. This is because the diameter of the atomic nucleus is of the order of 10-
14
m. Hence if the electron were to exist within the nucleus, the maximum uncertainty in its position
would have been 10-14 m. Taking the mass of electron as 9.1 × 10-31 kg, the minimum uncertainty in
velocity can be calculated by applying uncertainty principle as follows:–
x.p = h/4
or,x.mxv) = h/4
. ×
or,v = (h/4X = × . ×
= 6 x 109m/sec, which is much higher
×
than the velocity of light and hence is not possible.
b) With the help of this principle, it is possible to determine the limit to the accuracy with which we
can measure the frequency of radiation emitted by an atom.

Problem 1: Calculate the uncertainty in position of an electron if the uncertainty in velocity is
5.7 × 105 msec-1.
Problem 2: The uncertainty in position and velocity of a particle are 10-10m and 5.27 × 10-24 m
sec-1. Calculate the mass of the particle.
Schrodinger Wave Equation

According to Heisenberg’s Uncertainty Principle it is impossible to measure simultaneously the
position and momentum of an electron with accuracy. On this basis Bohr’s atomic model is no longer
correct. Therefore it is only possible to predict the probability of locating an electron with a probable
velocity with a particular energy in a given region of space at a given time – it is called the probability
approach. In order to provide sense and meaning to this approach, Schrodinger derived an equation
known as Schrodinger wave equation. He considered an electron wave of amplitude . If ‘x’ is the
displacement of the wave in x-direction and  is its wavelength, then  is given by:
= A sin
⇒ = cos ⇒ = − sin = − .
1
0
⇒ = − × …………………………………1
From de-Broglie’s Eqn.: = ℎ
Putting this value in Eq. 1, we get
⟹ = −
Now, KE= = =−
Total energy of a particle, E = KE + PE

or, KE = E – PE = −
or,− = − ( − )
or, + ( − ) = 0, this is 1-D Schrodinger wave equation.
+ + + ( − ) = 0, this is 3-D Schrodinger wave equation
∇2 ( − ) = 0, This is a one form of Schrodinger wave equation.
[∇2 = + + is called Laplacian operator]
+ +  ( − ) =0

or, ( − ) = -∇2
or, ( − ) =− ∇2 
or, − ∇ + 
The operator − ∇ + V is called Hamiltonian operator and is represented by Ĥ.
Thus, Ĥ = 
Schrodinger Equation being a second order differential equation can have many solutions for
the amplitude function but only those values of are acceptable and significance which correspond
to some definite values of the total energy E. Such values of the total energy E are called eigen values.
These values are also called proper values or characteristic values. The corresponding values of the
function are called eigen functions or wave functions. The eigen function (physically observable
system)  must satisfy the following conditions:
a. must be single valued and finite.
b. must be continuous.
c. must become zero at infinity.
d. , must be continuous functions of x, y and z respectively.
1
1
e. The function must be normalized.
Significance of  and 2
 has the following significances:
i. It represents the amplitude of an electron wave
ii. It is a solution to Schrodinger wave equation
iii. It describes the variation of amplitude of the wave with distance and direction
iv. Although  has a no. of values, the significant values are called Eigen functions and the
energy corresponding to these functions are known as Eigen values.
 2 has the following significances:

i. 2always has the positive value and hence measures the probability of finding the
electron at a point in space.
ii. A large value of 2 means a high probability of finding the electron at that place and a
small value of 2 means low probability. If  2 is almost zero at a particular point, it means
that the probability of finding the electron at that point is negligible.
iii. It is proportional to the probability density of the electron
iv. It leads to concept of orbital
[The function 2 is proportional to the probability density of the electron at a point in space. By
considering values of  2 at points in the volume of space about the nucleus, it is possible to define a
surface boundary that encloses the region of space in which the probability of finding the electron is,
say, 95%. By doing this, we are effectively drawing out the boundaries of an atomic orbital. Remember
that  2 may be described in terms of the radial and angular components R(r)2 and Y()2. Remember,
also, that these boundaries are only approximations; in principle, all orbitals are infinitely large]
Physical Significance of Wave Function 
In the physical sense,  gives the amplitude of the wave associated with the electron. It is

known that in case of light waves, the square of the amplitude of the wave at a point is proportional to
the intensity of light. Extending the same concept to electron wave motion, the square of the wave
function,  2 may be taken as intensity of electron at any point. In other words,  2 determines the
probability of finding the moving electron in a given region or it gives the probability density. Thus,  2
has been called the probability density and  the probability amplitude. Thus, the solutions of
Schrodinger wave equation replace the discrete energy levels or orbits proposed by Bohr and led to the
concept of most probable regions in space in terms of 2. A large value of 2 means a high probability of
finding the electron at that place and a small value of 2 means low probability. If 2 is almost zero at a
particular point, it means that the probability of finding the electron at that point is negligible.
Therefore, the wave mechanics approach gives meaningful wave functions, which describe the position
and energy levels of electrons in an atom.
Normalization
Wave functions are usually normalized to unity. This means that the probability of finding the
electron somewhere in space is taken to be unity, i.e. 1. In other words, the electron has to be
somewhere!
Mathematically, the normalization is represented by equation 3.6. This effectively states that we
are integrating (∫ ) over all space ( ) and that the total integral of  2 (which is a measure of the
probability density) must be unity.
∫ =1
1
2
Electron Probability Distribution Function, ‘D’
Problem with 2 is that it over estimates probability close to nucleus and underestimates the same
when it is further out from the nucleus. This problem is corrected by multiplying with 4r2dr.
Probability of finding an electron in a radial shell of radius r and thickness dr round the nucleus =
(probability density)2 × vol. of the radial shell =  2 × 4r2dr. Thus, the total probability of finding an
electron in space at a distance between r=0 to r=∞ (from the nucleus) would be: ∫ 4 dr = 1.
2 2
 4r is called probability distribution function (PDF) denoted by ‘D’.
The volume of the radial shell, V = ( + ) –
= + ( ) + ( )+ ( ) −
= ( ) + ( )+ ( )
≈ [Since ( ) and ( ) have very small
values]
Size and shape of atomic orbitals: Radial and Angular plots
According to wave mechanics, orbitals are described by wave functions known as orbital wave
functions. These orbital wave functions can be represented as a product of two functions: (i) Radial
wave function and (ii) Angular wave function.
The radial wave function depends upon the distance (r) from the nucleus whereas angular wave
function depends upon the direction given by angles with respect to different axes. The complete wave
function represents an orbital in which radial part gives the size and the angular part gives its shape. It is
observed that the wave function for s-orbital is independent of angles and therefore, s-orbitals do not
have angular dependence. Thus, all s orbitals are spherically symmetrical. However, all other types of

orbitals (p or d) have angular dependence and, therefore, have directional dependence.
+ + + ( − ) =0
In this equation Cartesian coordinates have been used. Converting them into spherical polar coordinates
using the following formulae:
x=r sin cos ∅, y=r sin sin ∅, z=r cos
i. r = distance from nucleus for the electron
ii.  = angle from the z-axis (from 0 to )
iii.  = angle from the x-axis (from 0 to 2
we get,
+ + +
+ + =0
In this equation the total wave function () is a function of three variables r, and . The
solution of the above equation therefore can be separated into the product of three functions R(r),
Θ( ) and Φ( ).

1
3
n,l,mr, , ) = R(r).Θ( ).Φ( ) = Rn,l(r). Ym,l()
A. The radial wave function Rn,l(r) describes the electron density at different distances from nucleus
 It depends only on the distance of the electron from the nucleus, and is characterized by the
two quantum numbers n and l.
 A particular distance from the nucleus (r) where Rn,l(r) is zero (and hence the probability of
finding the electron 2 is also zero) is called a radial (or spherical) node. Possible number of
radial nodes = (n-l-1).
 The radial wave-functions are of the general form: Rn,l(r) = Np(r)e-kr. ‘N’ is a positive
normalizing constant. ‘p(r)’ is a polynomial in r. ‘k’ is a positive constant.
 The exponential factor is always positive, so the radial nodes (where R(r)=0 & hence the
probability of finding the electron  2 is zero ) and sign of Rn,l(r)depends on the behavior of
p(r).
 Because the exponential factor has a negative sign in the exponent, Rn,l(r)approaches zero
as r goes to infinity.
Given below are some examples of the radial functions, Rn,l(r):

Note, Rn,l(r) depends on n and l but not on m.
Another important function we need to consider - radial probability distribution (RPD) function
denoted by Pn,l (r) or simply radial distribution function (RDF).
Radial probability gives the probability of finding an electron in a spherical shell of radius and
thickness and it is = Radial Probability Density x Volume of the radial shell = , ( ) × 4 .
Thus, the total radial probability of finding an electron in space at a distance between r=0 to r=∞ (from
the nucleus) would be: ∫ 4 , ( ) =∫ , ( ) =1 where Pn,l(r)= 4 , ( ) . The
2
factor 4πr arises because the radial distribution function refers to the probability of finding an electron
not at a specific point in space (which equals Ψ2), but on a spherical shell of area 4πr2, at a distance r
from the nucleus. The integral results from the fact that the total probability of finding the electron is
one, as it must be found somewhere around the nucleus. Due to multiplication by r2, by definition the
radial probability distribution function becomes independent of direction.
The plot of radial distribution function, 4 , ( ) for the 1s atomic orbital of the hydrogen
atom against appears as below:
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4
This function describes the probability of finding the electron at a distance r from the nucleus. The
maximum value of 4 , ( ) corresponds to the distance ( ) from the nucleus where there is the
maximum probability of finding the electron.
In the following section we find different sets of comparative plots for s-electrons, p-electrons and
d-electrons:

Important points to be noted about the 4 , ( ) vs. plots:
i. Radial probability distribution is always small near the nucleus {as 4 is small near the
nucleus}.
ii. All orbitals have radial probability = 0 at r = 0
iii. Curves start from the origin and the areas covered by envelops of a particular curve go on
increasing from left to right. So that the area of the last envelop is maximum.
iv. As we are dealing with a function containing , ( ) , the graph can never have negative values,
while the wave-function , ( ), can have both positive and negative amplitudes.
v. ns-electrons show high probability in very close vicinity of the nucleus ( ≅ )(presence of a well-
defined envelop structure at this position). On the other hand np-, nd- and nf-electrons have poor
probability at that same region (absence of any such well-defined envelop structure at that
position like s-electrons)(see the picture below).
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5
This means that ns-electron is more penetrating than np-electron. Similarly, np-electrons show
higher probability of density (indicated by small envelop structure) closer to the nucleus, in contrast
to, nd-electrons –this means np-electron is more penetrating than nd-electron. Thus penetration
power follows the following order: ns˃np˃nd˃nf. This is important for a discussion of the periodic
table and ionization energies.
vi. Electrons in orbitals with higher n are usually found with maximum probability further
from nucleus.
vii. Electrons in orbitals with same n are about same distance from nucleus.
viii. The point at which 4r2 , ( ) =0 is called a radial node. Notice that the value of zero at
the radial node is due to the function R(r) equaling zero, and not r=0 as was true at the
nucleus. The no. of radial nodes = (n-l-1).

ix. The number of radial nodes increases ongoing from the n-th orbital to the (n+1)-th orbital
and so on, since the number of radial nodes = ( n-l-1).
x. The greater the no. of radial nodes for an orbital, the bigger is the size of that orbital and it
becomes more diffused.
A plot of R vs. r⟹ Change of radial wave-function with change in r
A plot of R2 vs. r⟹change of electron density distribution with r
A plot of Pn,l(r) (=4r2R2)vs. r⟹Change of radial probability for electron density distribution
with r. The maximum value of 4r2R2 corresponds to the distance from the nucleus where there
is the maximum probability of ﬁnding the electron.
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‘In reality plot of Pn,l(r) vs. r is more justified than that of R(r) vs. r or , ( ) vs. r in predicting
probability of electrons’– Comment.

From the above plots it may be concluded that R(r) or R(r) cannot be probability density of any
electron at any point at a distance ‘r’ from the nucleus because of the following reasons:
i. For s-electrons R(r) always becomes max. at r≈0 that means if R(r) represents
probability density, then probability of finding the electron near nucleus is maximum.
This is against our experimental observation i.e. the actual probability of finding electron
at nucleus is zero.
ii. For s-electrons it is to be noted that R(r) holds both +ve and –ve value, but probability
density cannot be negative in reality.
iii. If probability density is related to ( ) instead of ( ) –in that case also it is clear that
for s-electrons still the curves show that the probability of finding electron is maximum
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at the nucleus (r≈0), which is not possible in reality although in this case the curves
never show any negative value.
This following box shows the shapes of the radial wave-

functions, Rnl(r), and the radial distribution functions,
Pnl(r), of the atomic orbitals.
Rnl(r) Pnl(r) n l
1s 1s 10
2s 2s 20
2p 2p 21
3s 3s 30

3p 3p 31
3d 3d 32
B. Angular distribution function

The angular wave function Ym,l() does much to give an orbital its distinctive shape.
Ym,l() is typically normalized so the integral of Y2m,l() over the unit sphere is equal to
one. In this case,Y2m,l()serves as a probability function. The probability function can be
interpreted as the probability that the electron will be found on the ray emitting from the origin
that is at angles ( , )from the axes. The probability function can also be interpreted as the
probability distribution of the electron being at position ( , ) on a sphere of radius r, given
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8
that it is r distance from the nucleus. It is observed that the wave function for s-orbital is
independent of angles and therefore, s-orbitals do not have angular dependence. Thus, all s orbitals are
spherically symmetrical. However, all other types of orbitals (p or d) have angular dependence and,
therefore, have directional dependence.
i. An s orbital (/ = 0) has the shape of a sphere. All s orbitals have spherically symmetrical
shape. They differ only in their size; higher the value of n, larger is the size of the sphere:
ii. The three p orbitals (I = 1) have dumbbell shape. These three orbitals differ from one
another in the directions in which their electron density is concentrated. They are called
px, py and pz orbitals. The energy of the three p-orbitals is the same and they are said to be
three fold degenerate.
iii. The five d orbitals (/ = 2) have slightly complicated shapes than the p orbitals. Four of the
d orbitals have a double dumbbell shape and the fifth one is like a dumbbell with a collar
at its center. They are designated as dxy, dyz, dxz, dx2 y2 and dz2 orbitals. The shapes of s, p
and d orbitals are shown in Fig. 8. The energy of five d-orbitals is the same and they are

said to be five fold degenerate.
Molecular Orbital Theory (MOT)

It is an approach to explain the formation of covalent bond. This theory is based on Linear
Combination of Atomic Orbitals (LCAO) of atoms constituting the molecule or ion. According to this
theory all the electrons in a given molecule or ion are considered to be present in MOs.The molecular
orbitals consist of nuclei of all constituent atoms lying at a fixed equilibrium distance.
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Feature of Molecular Orbital Theory:
The main features of the Molecular Orbital Theory are:
 The constituting atomic orbitals (AOs) lose their being identity.
 In a molecular orbital Theory, electrons revolve in the field of more than one nucleus
(polycentric).
 The number of molecular orbital is produced is equal to the number of overlap atomic orbitals.
 Filling up of the molecular orbitalsalso follows Pauli’s exclusion principle and Hund’s rule of
maximum multiplicity.
 Only those atomic orbitals can come together to form molecular orbitals which are analogous in
energies as well as of same symmetry. They combine linearly.
 Molecular orbital obtained by addition of atomic wave functions, (MO)= A + B is called
bonding molecular orbital.
 Molecular orbital obtained by subtraction of atomic wave functions, *(MO)= A - B is called
anti-bonding molecular orbital.
 Probability of bonding molecular orbital formation greater than that of anti-bonding molecular
orbital formation.
 The shape of the molecular orbital theory produced depends on the type of the combining
atomic orbitals.
 Inner molecular orbital theories which do not take part in bond formation are called non-
bonding molecular orbital theory.
Conditions for the Formation of Molecular Orbitals:
1. The combining atomic orbitals must be physically close enough to interact to the maximum
extent. The magnitude of the combination is inversely proportional to the distance between the
atoms.
2. The orbitals must combine along an axis of mutual symmetry. This means that the AOs having
the same or roughly the same energy will not overlap if they do not have the same symmetry.
The magnitude of the combination will be proportional to the cosine of the angle between the

orbitals if they are not perfectly aligned. Remember that Cos(0º) = 1 and Cos(900) = 0.
3. The orbitals must be similar in size and energy. The magnitude of the combination is inversely
proportional to the difference in size or energy.
Comparison between Atomic Orbital (AO) and Molecular Orbital (MO)

Similarities:
i. The MOs in a molecule or an ion have different energy and different shape and size as AOs in
atom have
ii. The filling of AOs with electrons with electrons takes place in accordance with Aufbou principle,
Pauli’s exclusion principle and Hund’s rule of maximum spin multiplicity.
iii. Like AOs a MO can be represented by a wave function .
iv. Each AO wave function in an atom is associated with a set of quantum numbers which
determine the energy and shape of AO. Similarly each MO in a molecule is also associated with a
set of quantum numbers which determine the energy, shape
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Dissimilarities:
Atomic Orbital Molecular Orbital
An AO is defined as the region of space round one nucleus in

An AO is defined as the region of space
an atom in which there is maximum probability of finding the
round two or more nuclei in a molecule.
electron.
They are formed when the lobes of the

They are formed when the lobes of the combining atomic
combining atomic orbitals have opposite
orbitals have same sign
sign
Atomic orbitals, solutions derived from the Schrödinger wave equation, are wave functions, where
waves are well understood mathematically. Waves can be added together or subtracted from each
other.
Likewise, atomic orbitals can be added together to give a superposition called a molecular orbital or
MO. Molecular orbitals are bonding when the orbital phase considerations are favorable. A bonding MO
shows a buildup of electron density between the two positively charged nuclei. If the atomic orbitals are
"out of phase" the AO/AO interaction will exhibit a phase node (a region in space with zero electron
density) between the positive nuclei. There will be nothing to attract the nuclei together and the MO is
called antibonding.
The following diagram shows the bonding and antibonding molecular orbitals formed from the
interaction of two 1s atomic orbitals.

Like 1s, 2s atomic orbital from one atom can overlap with the 2s from the other atom to form a
σ2s bonding molecular orbital and a σ*2s antibonding molecular orbital. Both σ2s and σ*2s molecular
orbitals are higher energy and
larger than the σ1s and σ*1s molecular orbitals.
The p atomic orbitals of the two atoms can interact in two different ways, parallel or end-on.
The molecular orbitals are different for each type of interaction. The end-on interaction between two
2px atomic orbitals yields sigma molecular orbitals, which are symmetrical about the axis of the bond.
The two 2py atomic orbitals overlap in parallel and form two  molecular orbitals (π2p and π*2p). 
molecular orbitals are asymmetrical about the axis of the bond.
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1
The 2pz-2pz overlap generates another pair of π2p and π*2p molecular orbitals.
There is less overlap for the parallel atomic orbitals. When the interaction is in-phase, less
overlap leads to less electron charge enhancement between the nuclei. This leads to less electron
charge between the nuclei for the pi bonding molecular orbital than for the sigma bonding molecular
orbital. Less electron character between the nuclei means less plus-minus attraction, less stabilization,
and higher potential energy for the pi bonding molecular orbital compared to the sigma bonding
molecular orbital.
When the interaction is out-of-phase, less overlap leads to less shift of electron charge from
between the nuclei. This leads to more electron charge between the nuclei for the pi antibonding
molecular orbital than for the sigma antibonding molecular orbital. More electron charge between the
nuclei means more plus-minus attraction and lower potential energy for the pi antibonding molecular
orbital compared to the sigma antibonding molecular orbital.
Characteristics of sigma-bonding MO () & sigma-antibonding MO (*):
i. Both &* molecular orbitals have cylindrical symmetry along the internuclear axis.
ii. In molecular orbital the density between the neclei of the combining atoms is very high
and hence this bond is stable enough. On the other hand In molecular orbital the
density between the neclei of the combining atoms is negligible and hence the nuclei fly
apart.
iii. The energy of -bonding MO () is less than the combining AOs while the energy of -
antibonding MO (*) is higher.

iv. -bonding MO () has no node while -antibonding MO (*) has one.
Characteristics of pi-bonding MO () & pi-antibonding MO (*):

i. Pi molecular orbitals are not symmetrical about the molecular axis.
ii. The electron density in pi-bonding MO () is zero on a plane that contains the nuclear axis
(nodal plane). The electron density is concentrated in the region above and below this
nodal plane. pi-antibonding MO (*) has the least electron density in the region between
the nuclei of the two atoms.
iii. Both &* molecular orbitals have the same energy and hence are called degenerate
orbitals.
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Molecular Orbitals from p A.O.s:
Difference between Bonding and Antibonding Molecular Orbitals

Bonding MO Antibonding MO
Bonding molecular orbital is formed by the addition of Antibonding molecular orbital is formed by the
overlapping of atomic orbitals. The wave function of the subtraction of overlapping of atomic orbitals. The wave
bonding MO may be written function for the antibonding MO may be written as:
as: Ψ(MO) = ΨA + ΨB Ψ (MO) = ΨA - ΨB
They are formed when the lobes of the combining They are formed when the lobes of the combining
atomic orbitals have same sign atomic orbitals have opposite sign

It has greater electron density in the region between the It has lesser electron density in the region between the
two nuclei of bonded atoms two nuclei of the atoms
The forces in this orbital tend to bring the two nuclei of The forces in this orbital push the nuclei apart.
the atoms together. Therefore, electrons in the bonding Therefore, the electrons in antibonding MO contribute
MO contribute to attraction between the two atoms to repulsion between the atoms
It possesses lower energy than the isolated atomic It possesses higher energy than the isolated atomic
orbitals orbitals
Molecular Energy Level Diagram for Diatomic Molecules:

The following rules are followed for filling up molecular orbitals with electrons in order to write
molecular configurations:
1. The molecular orbital having the lowest energy is filled first. This is in accordance with Aufbau
principle as already discussed for atoms.
2. Each molecular orbital can accommodate maximum of two electrons having opposite spins. This
is in accordance with Pauli's exclusion principle.
3. If there are two molecular orbitals of the same energy, the pairing of electrons will occur only
after each orbital of same energy has one electron. This is in accordance with Hund's rule.
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3
General MO diagram for the diatomic molecules X2 (Li2 to N2; note that this diagram is valid for diatomic
molecules having total no of valance electrons upto 10):
The diagram is only showing the MO’s derived from the valence electrons because the pair of
MO’s from the 1s orbitals are much lower in energy and can be ignored.
Most importantly, the ordering of the 2 orbitals is changed 2py)=2pz)<2px) because of
mixing between the 2s and 2pX atomic orbitals. From Quantum mechanics: the closer in energy a given
set of orbitals of the same symmetry, the larger the amount of mixing that will happen between them.
These mixing changes the energies of the MO’s that are produced.
General MO diagram for the diatomic molecules X2 (O2 and F2 and NO; this diagram is valid for
diatomic molecules having total no of valance electrons beyond 10):
Notice that beyond nitrogen there is no mixing of 2s and 2pX AO’s of the same symmetry from a single X
atom because there is a sufficient difference in energy between the 2s and 2p orbitals. Also notice that
the more nodes an orbital of a given symmetry has, the higher is the energy.
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4
We describe the stability of the molecule with bond order.
Bond Order (BO) = 1/2 (no of e’s- in bonding MO's - no of e’s- in antibonding MO's)
We use bond orders to predict the stability of molecules.
 If the bond order for a molecule is equal to zero, the molecule is unstable.
 A bond order of greater than zero suggests a stable molecule.
 The higher the bond order is, the more stable the bond.
We can use the molecular orbital diagram to predict whether the molecule is paramagnetic or
diamagnetic. If all the electrons are paired, the molecule is diamagnetic. If one or more electrons are
unpaired, the molecule is paramagnetic.
Molecule Be2: Total 4 electrons in the valance-shell (Be-atom: 2s2):-

2s) <2s) : BO = (2-2)/2 = 0, Zero value of BO implies that Be2 molecule does not exist.
Molecule B2: Total 6 electrons in the valance-shell (B-atom: 2s2 2p1):-
2s) <2s) <2py) = 2pz): BO = (4-2)/2 = 1, Magnetic Property: Paramagnetic (two unpaired e’s)
Molecule C2: Total 8 electrons in the valance-shell (C-atom: 2s2 2p2):-

2s) <2s) <2py) = 2pz): BO = (6-2)/2 = 2, Magnetic Property: Diamagnetic
Molecule N2: Total 10 electrons in the valance-shell (N-atom: 2s2 2p3):-

2s)<2s)<2py)=2pz)<2px): BO = (8-2)/2 =3; Magnetic Property: Diamagnetic
Structure:
N2+ ion: Total 9 electrons in the valance-shell (N-atom: 2s2 2p3):-

2s)<2s)<2py)=2pz)<2px): BO = (7-2)/2 =2.5, Since the BO of N2 is greater than that of N2+ the N2
molecule is more stable than N2+. Magnetic Property: Paramagnetic (one unpaired ‘e’).
Structure:
O2 molecule: Total 12 electrons in the valance-shell (O-atom: 2s2 2p4):-

2s)<2s2px)<2px)<2py)=2pz)<2py)=2pz): BO = (8-4)/2 =2, Magnetic Property: Paramagnetic
(two unpaired ‘e’s). Structure:
O2+ ion: Total 11 electrons in the valance-shell (O-atom: 2s2 2p4):-
2s)<2s)<2px)<2py)=2pz)<2py): BO = (8-3)/2 =2.5, Since the BO of O2 is lower than that of O2+ -
the O2 molecule is less stable than O2+ ion. Magnetic Property: Paramagnetic (one unpaired ‘e’).
Structure:
O2-1 ion (superoxide ion): Total 13 electrons in the valance-shell (O-atom: 2s2 2p4):-
2s)<2s)<2px)<2py)=2pz)<2py) = 2pz): BO = (8-5)/2 =1.5, Since the BO of O2 is more than that
of O2- - the O2 molecule is more stable than O2- ion. Magnetic Property: Paramagnetic (one unpaired ‘e’).
Structure:
O2-2 ion (peroxide ion): Total 14 electrons in the valance-shell (O-atom: 2s2 2p4):-
2s)<2s)<2px)<2py)=2pz)<2py) = 2pz): BO = (8-6)/2 =1.0, Since the BO of O2 is more than that
of O22- - the O2 molecule is more stable than O22- ion. Magnetic Property: Diamagnetic.
Structure:
So the stability of the four species is in the order: O2+˃O2˃O2-˃O22-, while the O-O bond length is in the
order O2+<O2<O2-<O22-.
Molecule CO: Total 10 electrons in the valance-shell (C-atom: 2s2 2p2, O-atom: 2s2 2p4):-
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5
2s)<2s)<2py)=2pz)<2px): BO = (8-2)/2 =3; Magnetic Property: Diamagnetic. Note that energy of
AOs of C is higher than that of O.
Molecule NO: Total 11 electrons in the valance-shell (N-atom: 2s2 2p3, O-atom: 2s2 2p4):-
2s)<2s)<2px)<2py)=2pz)<2py): BO = (8-3)/2 =2.5; Magnetic Property: Paramagnetic (one
unpaired ‘e’). Note that energy of AOs of N is higher than that of O.
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Molecule HF: Total 8 electrons in the valance-shell (H-atom: 1s1, F-atom: 2s2 2p5):- nb<<nb=nb:
BO = (2-0)/2 =1
Exercise:
 Explain why N2 molecule is more stable than NO molecule?
 Explain why IE of N2 molecule is higher than that of N2 molecule as well as that of NO molecule.
 The IE of O2 molecule is less than that of O2+ ion.
 H2 molecule is more stable than H2+ ion.
 He2 and Be2 molecules do not exist.

Metallic Bonding
Metals are solids at ordinary temperature and pressure, with the exception (of mercury and gallium).
Metals have characteristic properties such as:
 High thermal and electrical conductivity.
 Luster and high reflectivity.
 Malleability and ductility. They can be beaten or shaped without fracture.
 Variability of mechanical strengths (ranging from soft alkali metals to Tungsten, which is hard).
In metals large interatomic forces are created by the sharing of electrons in a delocalized manner to
form strong non-directional bonding. This force that binds together the atoms of metals is called
metallic bond. The properties of metals cannot be explained in terms of common types of bonds such as
ionic and covalent bonds. The inadequacy of these two types of bonds for metal formation can be
explained as under.
The atoms of metals are all alike therefore they cannot form ionic bonds. Moreover, ionic
compounds do not conduct electricity in the solid state and ionic compounds are brittle as opposed to
properties of metals. The atom of metallic elements contain only 1 to 3 valence electrons, therefore
these atoms cannot form covalent bonds, with noble gas configurations as they will remain incomplete.
Covalent compounds are bad conductors of electricity and are generally liquids; properties opposed to
metal formations. Thus, metals have a different model of bonding.
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Characteristics of Metallic Bond Formation
 Metallic bond is formed by mutual attraction between mobile electrons and positive metal ion
layers.
 Metallic bond is weaker because valence electrons are mobile and weakly attracted by metal
ions.
 Bond is present around identical metal ions.
 Metallic bond is weaker because mobile electrons are weakly attracted by metal ions.
The strength of metallic bond formation depends on:
 Number of valence electrons.
 Charge on the metal ions.
 Size of the metal ions.
Metallic bond is weaker in alkali metals because of:
 Only one valence electron on each metal atom.
 One positive charge on the metal ion.
 Larger size of the metal ion.
(A) Electron sea model for metallic bonding

To account for the bonding in metals, a model known as electron gas model or electron sea
model is proposed. This model is based on the following characteristic properties of metals:
i. Low ionization energies
Metals generally have low ionization energies. This implies that the valence electrons of metal atoms
are not strongly held by the nucleus. Valence electrons can move freely out of the influence of their
kernels (atomic orbit/structure minus valence electrons). Thus, metals have free mobile electrons.
ii. Large number of empty orbitals
It has been observed that in metals a number of valence orbitals remain empty as the number of
valence electrons in metals is generally less than the number of valence orbitals.

For example, lithium {(Li, Z = 3) 1s22s1} has 2p-orbitals vacant;
Sodium {(Na, Z = 11) 1s22s22p6 3s1} has 3p-and 5d-orbitals vacant;
Magnesium {(Mg, Z = 12) 1s22s22p6 3s2} has 3p-and 3d-orbitals vacant
The important features of electron sea model are:

 The positively charged kernels of metal atoms are arranged in a regular fashion in a metallic
lattice.
 Loosely held valence electrons, surround each kernel in metallic lattice. Being loosely held to its
kernel, the valence electrons enjoy complete freedom in the metallic lattice and are regarded as
mobile electrons.
In short, the metal may be regarded as 'a sea of loosely held electrons (common pool of electrons) in
which there is a three dimensional ordered arrangement of positively charged kernels, surrounded
throughout by mobile valence electrons'. This explanation is also responsible for its name electron sea
model.
Thus, the simultaneous force of attraction between the mobile electrons and the positive kernels that
binds the metal atoms together is known as metallic bond.
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Explanation of physical properties of metals
All the characteristic metallic properties can be explained on the basis of the electron sea model.
a) Metallic luster
The bright luster of metals is due to presence of delocalized mobile electrons.
When light falls on the surface of the metal, the loosely held electrons absorb photons of lights. They get
promoted to higher energy levels (excited state), oscillating at a frequency equal to that of the incident
light. These oscillating electrons readily return from the higher to the lower levels of energy by releasing
energy, thus becoming a source of light radiations. Light appears to be reflected from metal surface and
the surface acquires a shining appearance, which is known as metallic luster.
b) Electrical conductivity
The presence of mobile electrons causes electrical conductivity of a metal. When a potential
difference is applied across the metal sheet, the free mobile electrons in the metallic crystal start
moving towards the positive electrode. The electrons coming from the negative electrode
simultaneously replace these electrons. Thus, the metallic sheet maintains the flow of electrons from
negative electrode to positive electrode. This constitutes electrical conductivity.
c) Thermal conductivity
When a part of the metal is heated, the kinetic energy of the electrons in that region increases. Since
the electrons are free and mobile, these energetic electrons move rapidly to the cooler parts and transfer

their kinetic energy by means of collisions with other electrons. Therefore, the heat travels from hotter to
cooler parts of the metals.
d) Malleability and ductility
Metals can be beaten into sheets (malleability) and drawn into wires (ductility). Metallic bonds
are non-directional in nature. Whenever any stress is applied on metals, the position of adjacent layers
of metallic kernels is altered without destroying the crystal. The metallic lattice gets deformed but the
environment of kernels does not change and remains the same as before. The deforming forces simply
move the kernels from one lattice site to another.
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9
e) High tensile strength
Metals have high tensile strength. Metals can resist stretching without breaking. A strong
electrostatic attraction between the positively charged kernels and the mobile electrons surrounding
them is the reason for tensile strength.
f) Hardness of metals
The hardness of metals is due to the strength of the metallic bond. In general, the strength of a
metallic bond depends upon:
 The greater the number of valence electrons for delocalization the stronger is the metallic bond.
 Smaller the size of the kernel of metal atom, greater is the attraction for the delocalized
electrons. Consequently, stronger is the metallic bond.
For example, alkali metals have only one valence electron and larger atomic kernels, which makes the
metallic bonds weak. Consequently these metals are soft metals.
g) Opaqueness
The light that falls on metals is either reflected or completely absorbed by the delocalized
electrons. Because of this, no light is able to pass through metals and they are termed as opaque.
h) Melting and boiling points

Metals have metallic bond strengths, which is intermediate to that of covalent and ionic bonds.
Therefore in general, metals have boiling and melting points in between to that of covalent and ionic
compounds.
(B) Molecular Orbital Model

The most useful treatment of metallic solids is based on the molecular orbital approach.
i. Metals are held together by delocalized bonds formed from the atomic orbitals of all the
atoms in the lattice.
ii. The orbitals spread over many atoms and blend into a band of molecular orbitals. The range of

energies of these orbitals is closely spaced.
iii. The band is composed of as many levels as there are contributing atomic orbitals and each
level can hold electrons of opposite spin. This theory of metallic bonding is called the band
theory.
iv. The band is split into two regions, the upper portion being the empty levels or the antibonding
and the lower portion is the filled levels or the bonding orbitals.
v. The band is split into two regions, the upper portion being the empty levels or the antibonding
and the lower portion is the filled levels or the bonding orbitals.
vi. In a metal the band of energy levels is only partly filled. The highest filled level right before
going to the empty level is called the Fermi level. The trend of melting points of the transition
metals is based on the electrons in the metal.
Band Theory of Bonding in Solids
Bonding in solids such as metals, insulators and semiconductors may be understood most effectively
by an expansion of simple MO theory to assemblies of scores of atoms. In simple MO theory it is
assumed that atomic orbitals on two atoms could come together to form bonding and antibonding
orbitals.
3
0
If this is expanded to a molecule with three atoms, assuming 1 atomic orbital for each, then the
result must be that 3 molecular orbitals will be formed: one bonding, one non-bonding and one anti-
bonding.
Now, let's take it to 10 atoms. This will produce 10 molecular orbitals: 5 bonding and 5 anti-bonding.
Now let’s take a close look at the separation between each set of orbitals. As the number of molecular
orbitals inceases, the energy difference between the lowest bonding and the highest antibondig
increases, while the space between each individual orbital decreases. As the number of molecular
orbitals increses with the number of atoms in a molecule, it will the observed that the spacing between
the lowest bonding and highest antibonding orbital will reach a maximum.

Now consider a metal with an infinite number of atoms. This will form an infinite number of molecular
orbitals so close together they blur into one another forming a band. This whole process is shown
below.
3
1
We thus have a huge number of MOs crammed into a finite energy interval. They will be so close
together in energy that they will form, for all practical purposes, a continuous band of energy levels. For
this reason the MO theory of solids is often called Band Theory. A very important result of this
treatment is that each of the MOs in the band is delocalized over all of the atoms in the chain.
Because of the very large number of atoms that interact in a solid material, the energy levels are
so closely spaced that they form bands. The highest energy filled band, which is analogous to the highest
occupied molecular orbital in a molecule (HOMO), is called the valence band. The next higher band,
which is analogous to the lowest unoccupied molecular orbital (LUMO) in a molecule, is called the
conduction band. The energy gap present between the valance and conduction band is called forbidden
energy gap, Eg.
Substance having large conductivity and negligible resistivity are called conductors for example,
gold, silver, copper etc. Conductors have a very large conduction band because of their conductivity. In
conductors, valence band is very small (almost empty). Forbidden band does not exist in conductors.
The valence band and conduction band overlapped each other. It means some of the electrons have
energies which lie simultaneously in valence band and conduction band. Moreover, on the average
there are 1023 free electrons per centimeter cube in a conductor.
The Fermi Level is defined as the highest occupied molecular orbital in the valence band at 0 K,
so that there are many states available to accept electrons, if the case were a metal. It should be noted
that this is not the case in insulators and semiconductors since the valence and conduction bands are
separated. Therefore the Fermi-Level is located in the band gap. It can be seen in the diagram below.
The probability of the occupation of an energy level is based on the Fermi function, but this will not be
discussed at length at this level.

If the Fermi level occurs in the middle of an allowed band, then the solid is a conductor. Some
examples of conductors are the metals silver and copper. With the Fermi level in the middle of an
allowed band, even small energies can excite electrons in the highest filled level to the lowest
unoccupied level. This mobility of the electrons gives conductors their defining qualities, such as their
ability to conduct electricity and heat, their ability to absorb light, and their opacity.
If the Fermi level occurs at the top of an allowed band, and there is a relatively large gap
between this and the next higher-energy allowed band, then the solid is an insulator, like diamond or
quartz. Because only large energies can excite the electrons, an insulator is a poor conductor of heat and
electricity, cannot absorb light, and is transparent.
Finally, if the Fermi level is near the top of a band but there is only a narrow forbidden energy
gap above it, then the solid is a semiconductor, like silicon.
3
2
Conductor, Insulators and Semiconductors — Explanation using Band Theory
We can use band theory to explain why some substances are electrical conductors, some are
not, and some are semiconductors. In the metals, bands overlap and allow a free movement of
electrons. In nonmetals, bands are widely separated, so no electron movement can occur (Figure 4.5a).
These elements are called insulators. In a few elements, the bands are close enough to allow only a
small amount of electron excitation in an upper unoccupied band (Figure 4.5b).These elements are
known as intrinsic semiconductors. Our modern technology depends on the use of semiconducting
materials, and it has become necessary to synthesize semiconductors with very specific properties. This
can be done by taking an element with a wide band gap and “doping” it with some other element, that
is, adding a trace impurity. The added element has an energy level between that of the filled and empty
energy levels of the main component (Figure 4.5c). This impurity band can be accessed by the electrons
in the filled band, enabling some conductivity to occur. By this means, the electrical properties of
semiconductors can be adjusted to meet any requirements
Conductors. Conductors are substances which allow the flow of electric current through them.
In a conductor the valence band and the conduction band overlap. So no energy is required to move the
electron from valence band to conduction band. Free electrons are available in conduction band and
thus current flows through it, when a p.d is applied across it [see Fig. 34.6 (a)]. Examples for conductors
are silver, copper, aluminium etc.
Insulators. Insulators are substances which do not allow the flow of electric current through
them. Examples are dry wood, glass, diamond etc. In insulators the valence electrons are very rigidly

held in the interatomic band, even at high temperatures.
In terms of band theory, insulators have a large energy gap between conduction band and the
valence band (greater than 5 eV). So electrons cannot jump from the valence band into the conduction
band. In the case of diamond the energy gapis 6 eV and hence no current conduction is possible
Semiconductors. Semiconductor is a substance whose conductivity lies in between that of a good
conductor and an insulator. Examples are germanium and silicon.
In terms of band theory, semiconductors have a small energy gap between conduction band and the
valence band. At 0 K, the energy gap is 0.785 eV for germanium and 1.21 eV for silicon. This decreases
with increase in temperature. At 0 K, the conduction band is empty and the semiconductor behaves as
an insulator. With increase in temperature electrons ftom valence band jump to conduction band and
hence current conduction is possible. Since the energy gap Eg is small [see Fig. 34.6 (c)], the number of
electrons jumping to the conduction band is greater, compared to insulator. When electrons jump from
valence band, to conduction band, it leaves some energy level in the valence band unfilled. This electron
missing site in the valence band is called a hole.
3
3
Intrinsic and Extrinsic Semiconductor
Semiconductor in the pure form is called intrinsic semiconductor. Examples are
germanium and silicon.
An extrinsic semiconductor is a semiconductor that has been "doped", that is, into which a
doping agent has been introduced, giving it different electrical properties than the intrinsic (pure)
semiconductor. Doping involves adding dopant atoms to an intrinsic semiconductor, which changes the
electron and hole carrier concentrations of the semiconductor at thermal equilibrium. Dominant carrier
concentrations in an extrinsic semiconductor classify it as either an n-type or p-type semiconductor. The
electrical properties of extrinsic semiconductors make them essential components of many electronic
devices.
Semiconductor doping is the process that changes an intrinsic semiconductor to an extrinsic
semiconductor. During doping, impurity atoms are introduced to an intrinsic semiconductor. Impurity
atoms are atoms of a different element than the atoms of the intrinsic semiconductor. Impurity atoms
act as either donors or acceptors to the intrinsic semiconductor, changing the electron and hole
concentrations of the semiconductor. Impurity atoms are classified as donor or acceptor atoms based
on the effect they have on the intrinsic semiconductor. Donor impurity atoms have more valence

electrons than the atoms they replace in the intrinsic semiconductor lattice. Donor impurities "donate"
their extra valence electrons to a semiconductor's conduction band, providing excess electrons to the
intrinsic semiconductor. Excess electrons increase the electron carrier concentration (n0) of the
semiconductor, making it n-type.
Acceptor impurity atoms have less valence electrons than the atoms they replace in the intrinsic
semiconductor. They "accept" electrons from the semiconductor's valence band. This provides excess
holes to the intrinsic semiconductor. Excess holes increase the hole carrier concentration (p0) of the
semiconductor, creating a p-type semiconductor.
Semiconductors and dopant atoms are defined by the column of the periodic table of elements
they fall in. The column definition of the semiconductor determines how many valence electrons its
atoms have and whether dopant atoms act as the semiconductor's donors or acceptors. Group IV
semiconductors use group V atoms as donors and group III atoms as acceptors.
Group III-V semiconductors use group VI atoms as donors and group II atoms as acceptors.
Group III-V semiconductors can also use group IV atoms as either donors or acceptors. When a group IV
atom replaces the group III element in the semiconductor lattice, the group IV atom acts as a donor.
Conversely, when a group IV atom replaces the group V element, the group IV atom acts as an acceptor.
Group IV atoms can act as both donors and acceptors; therefore, they are known as amphoteric
impurities.
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4
Thermal properties of semiconductors
At absolute zero, all of the charge carriers reside in lower of the bands below the small band gap
in a semiconductor (that is, in the valence band of the illustration on the left above, or in the impurity
band of the one on the right.) At higher temperatures, thermal excitation of the electrons allows an
increasing fraction jump across this band gap and populate either the empty impurity band or the
conduction band as shown at the right. The effect is the same in either case; the semiconductor
becomes more conductive as the temperature is raised. Note that this is just the opposite to the way
temperature affects the conductivity of metals.
n- and p-type materials

For example, a phosphorus atom introduced as an impurity into a silicon lattice
possesses one more valence electron than Si. This electron is delocalized within the impurity band and
serves as the charge carrier in what is known as an N-type semiconductor. In a semiconductor of the P-
type, the dopant might be arsenic, which has only three valence electrons. This creates what amounts to
an electron deficiency or hole in the electron fabric of the crystal, although the solid remains electrically
neutral overall. As this vacancy is filled by the electrons from silicon atoms the vacancy hops to another
location, so the charge carrier is effectively a positively charged hole, hence the P-type designation.
3
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Black Body Spectrum: Failure of Classical Mechanics

Blackbodies absorb and incandescently re-emit radiation in a characteristic, continuous spectrum. A

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

The graph shows:

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

At lower wavelength (higher frequency) T is small, ≫ 1, so at lower wavelength Plank’s

Explanation of Blackbody radiation by quantum mechanics:

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Significance of Photoelectric Effect

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

⇒ 1 (cm-1) = − = − , R=Rydberg Constant = 109,677cm-1

1/frequency of the line spectrum in cm-1.

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Significance of de-Broglie Equation

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Justification of Dual Character

Derivation of Bohr’s postulate of angular momentum from de Broglie equation

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Heisenberg’s Uncertainty Principle is important for small particles:-

Application of Heisenberg’s uncertainty principle:-

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Schrodinger Wave Equation

Putting this value in Eq. 1, we get

Total energy of a particle, E = KE + PE

or, + ( − ) = 0, this is 1-D Schrodinger wave equation.

+ + + ( − ) = 0, this is 3-D Schrodinger wave equation

∇2 ( − ) = 0, This is a one form of Schrodinger wave equation.

[∇2 = + + is called Laplacian operator]

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

 2 has the following significances:

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

The volume of the radial shell, V = ( + ) –

≈ [Since ( ) and ( ) have very small

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

This following box shows the shapes of the radial wave-

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

B. Angular distribution function

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Molecular Orbital Theory (MOT)

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Comparison between Atomic Orbital (AO) and Molecular Orbital (MO)

An AO is defined as the region of space round one nucleus in

They are formed when the lobes of the

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Characteristics of pi-bonding MO () & pi-antibonding MO (*):

Difference between Bonding and Antibonding Molecular Orbitals

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Molecular Energy Level Diagram for Diatomic Molecules:

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Molecule Be2: Total 4 electrons in the valance-shell (Be-atom: 2s2):-

Molecule C2: Total 8 electrons in the valance-shell (C-atom: 2s2 2p2):-

Molecule N2: Total 10 electrons in the valance-shell (N-atom: 2s2 2p3):-

N2+ ion: Total 9 electrons in the valance-shell (N-atom: 2s2 2p3):-

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding

Dr. Indrajit Chakraborty/Chemistry/Ch.2/Structure & Bonding