ATOMIC STRUCTURE AND CHEMICAL BONDING

SYLLABUS

Dual nature of matter and radiation. Heisenbergs Uncertainty principle Quantum mechanics Quantum Mechanical Treatment of the Hydrogen atom. Atomic orbitals and their pictorial Representation. Electronic configuration of Elements. Chemical Bonding. Molecular Orbital Theory. Bonding in some Homonuclear Diatomic molecules. Metallic Bonding. Hybridisation. Intermolecular forces.

DUAL NATURE OF RADIATION Albert Einstein in 1905 , suggested that light has a dual character, i.e., it can behave as a particle as well as wave. It was realized that some of the experimental facts regarding light could be explained only by assuming light to have wave like character while some other experimental facts could only be explained by assuming particle like character for light radiations.
Wave like character of radiation

Wave like character of light was proposed by Huygens. With the help of wave theory of light, Huygens explained the important phenomena of light such as reflection, refraction, diffraction and interference. In 1856, James Maxwell proposed that light and other forms of radiation propagate through the space in the form of waves and these waves have electric and magnetic fields associated with them. Therefore, these radiations are known as

electromagnetic radiations or electromagnetic waves. Thus electromagnetic radiation is a form of energy

which propagates through the space in the form of waves having electric and magnetic fields associated with them .
Limitations of wave character of radiation

The wave character of radiation failed to explain many phenomenon such as : (i) (ii) Black body radiation Photoelectric effect
Black body radiation

An ideal black body is defined as a perfect emitter of radiations. This means that a black body absorbs all the radiations falling on it. When such a body is heated, it emits radiations and it has been observed that no other body can emit radiant energy more than a black body. Hence a black body is the most efficient absorber radiant energy and it is also the most perfect emitter. This behaviour of black body

could not be explained on the basis of wave character of radiation.

Photoelectric effect

When a beam of light falls on certain metal plates in vaccum , the plates emit electrons. This effect was discovered by Hertz and is known as
Photoelectric Effect.

Photoelectric effect may be defined as the phenomenon of ejection of electrons from the surface of a metal when light of suitable frequency strikes it. The electrons, thus ejected are called photoelectrons.

It must be noted that the photoelectric effect is shown by any metal in a photoelectric cell only. The apparatus showing photoelectric effect is given in Fig 1. It comprises an evacuated tube with metal having low ionisation energy and constituting the negative electrode. Now light of sufficiently high energy strikes the metal, electrons are knocked off from its surface and move towards the positive electrode. The electrons constitute a current flowing through

the circuit. Only a few metals show this effect under the action of visible light. Caesium with lowest ionisation energy emits electrons very easily. Some important observations about photoelectric effects are :

(i)

For a particular metal, there exists a threshold frequency such that, at frequencies below threshold, no electrons are emitted, no matter how large, the intensity is or how long the radiation occurs.

ii)

The maximum kinetic energy of photoelectrons is directly proportional to the frequency of the incident radiation, but is independent of its intensity.

iii) The number of photoelectrons emitted per second is directly proportional to the intensity of
the incident radiation but does not depend upon its frequency. All these observations could not be explained on the basis of classical wave theory of light. According to classical theory, radiant energy is continuous and therefore , radiation of any frequency should have been able to bring about the ejection of the electrons simply by increasing the intensity of radiation. But all the experimental observations were contrary to what we expected.

Particle like character

The failure of classical electromagnetic theory to explain photoelectric effect led to the postulation of Plancks quantum theory of radiation.
Plancks Quantum Theory of Radiation

Planck in 1901 , gave a new theory of radiation known as quantum theory of radiation. The main features of the theory are given below : (i) Radiant energy is not emitted or absorbed continously but discontinuously in the form of small packets of energy called quanta. Each wave packet or quantum is associated with definite amount of energy. In the case of light, the quantum of energy is often called photon. (ii) The amount of energy associated with a quantum of radiation is proportional to the frequency of radiation and is expressed as :

E h E= h

Where h is a fundamental constant known as Plancks constant and is the frequency of radiation. The numerical value of h is equal to 6.626 x 1034 J s. (iii) A body can emit or absorb energy only in terms of whole number multiples of quantum, i.e., E = n h where n = 1, 2, 3. 4 , This means that a body can emit or absorb energy equal to h , 2 h , 3 h , .or any other integral multiple of h but it cannot emit or absorb energy equal to 1.6 h or any other fractional value of , h . From Plancks quantum theory of radiation, it may be concluded that radiations from any source do not represent a continuous flow of electromagnetic waves but a stream of individual tiny bundles of discrete energies called quanta or photons. This suggests that the light should have corpuscular or particle character.
Explanation of Photoelectric Effect

Einstein used the concept of quantum theory for explaining photoelectric effect and considered light as having a dual character- wave as well as particle. When light falls on the metallic surface , a photon of light is absorbed , which interacts with the most loosely bound electron in the metal surface, thereby parting-with all its energy. Part of this energy acquired by electron is just sufficient to separate itself from the metal surfaces ; while the remaining energy appears in the form of kinetic energy of the ejected electron. Thus : Energy of the photon = ( Threshold energy ) + (K.E acquired by electron ejected) h K.E = h o + = h h o

m v2 .

The validity of the above expression was tested by Millikan by calculating the value of h. It was found to be 6.57 x 1034 J s.

Since

for

particular

metal o and h are

constants,

so

kinetic

energy

of

photoelectrons is directly proportional to frequency. Kinetic energy of photoelectrons is independent of intensity because increase in intensity does not effect the energy of photons rather it simply increases the number of photons falling on the surface of metal and hence increases the number of photoelectrons. The photoelectric effect supports the particle nature of light because only a light of suitable frequency and not of any frequency can bring about the emission of photoelectrons. Also, increasing the frequency of radiation increases the velocity of electrons whereas increasing the intensity does not change it.
DUAL NATURE OF MATTER OR ELECTRON

When an electron was discovered , the various experiments carried out to characterize it (like Thomsons experiments, Millikans oil drop experiments) showed that an electron behaves as a particle. In Bohrs theory , electron is treated as a particle. However, in 1924 , Louis de Broglie suggested that just as light exhibits wave and particle properties, all microscopic material particles such as electrons, protons, atoms, molecules, etc. have also dual character. According to de Broglie, all material particles in motion also possess wave characteristics.
de Broglie Equation

According to de Broglie, the wave length associated with a particle of mass m, moving with velocity v , is given by the relation,

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