Rutherford's Atomic Model

Based on his scattering experiments, Rutherford suggested that an atom consists of :

 A minute positively charged body located at the center, called the nucleus. in which almost the entire mass of
the atom is concentrated. Since the mass of an atom is almost entirely due to protons, all the protons are
present in the nucleus.
 An equal number of extremely small negatively charged electrons distributed around the nucleus to balance
its positive charge.
 Rutherford proposed that the electrons are revolving round the nucleus at extremely high speeds at great
distances from the nucleus. The centrifugal force arising from this motion balances the force of electrostatic
attraction. The electrons, therefore do not fall into the nucleus.

1
 Objection of the Rutherford's Atomic Model
It was pointed out by Niels Bohr (the Danish physicist) that Rutherford's atom should be highly
unstable. Because J. C. Maxwell (the great Scottish mathematical physicist), had shown a few years
earlier that whenever an electric charge is subjected to acceleration, it emits radiation and loses energy.
Bohr argued, therefore, that if an electron (a charged particle) moves round the nucleus in an
orbit, as in Rutherford's model, it should be subjected to acceleration.
The electron should therefore, continuously emit radiation and lose energy. As a result, its orbit
should become smaller and smaller and finally it should drop into the nucleus. This, however, does not
happen.

2
 Bohr solved this problem on the basis of the quantum theory of radiation put forth by the German
physicist Max Planck to explain the observed distribution of energy in the spectrum of the heat radiations
emitted by a hot body.
Black Body: Any body that absorbs the energy of any radiation (all wavelengths of light) is called a black
body. It is not necessary that the color of a black body is black. The absorption coefficient of black body is 1.
 For each temperature, there is a
particular wavelength at which the
energy radiated is the maximum.
 The position of the maximum shifts
towards lower wavelengths with
increase in temperature.
𝟏
 𝝀 ∝ 𝑻 or 𝝀𝑻 = 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
 The higher the temperature, the more
pronounced is the maximum.
 These curves are referred to as the
black body radiation curves.
 A perfect absorber is also a perfect
emitter of radiation if temperature of
the body does not increases according
3
to Kirchhoff’s study.
 Thus, of all bodies heated to a given temperature, maximum energy is radiated by a black body.
According to Wien's displacement law, 𝝀𝒎𝑻 = 𝒃, where 𝝀𝒎 is the wavelength corresponding to the
maximum in the curve. The Wien’s constant b = 0.0029 mK or 0.29 cmK.
Quantum Theory of Radiation
The energy distribution in black body radiations could not be explained by the application of classical
physics. The correct expression was derived by Planck on the basis of the quantum theory of radiation.
According to this theory:
 Radiant energy is emitted or absorbed discontinuously in the form of tiny bundles of energy known as
quanta.
 Each quantum is associated with a definite amount of energy 𝑬(𝒉𝒗) where E is the energy in Joules, 𝒗 is
the frequency of radiation in reciprocal seconds (s-1) and h is a fundamental constant known as Planck's
−
constant. The numerical value of h is 𝟔 · 𝟔𝟐𝟔 × 𝟏𝟎 𝟑𝟒 𝑱 𝒔.
The value of a quantum of energy is also given by 𝒉𝒄𝝂 where 𝜈̅ is the wave number defined as the
𝟏 𝒄
reciprocal of wavelength i.e., 𝝂 = 𝝀 . Evidently, 𝝂 = 𝝀 = 𝒄𝝂 and 𝑬 = 𝐡𝒄𝝂
 A body can emit or absorb energy only in whole number multiples of quantum,
i.e.,𝟏𝒉𝒗, 𝟐𝒉𝒗, 𝟑𝒉𝒗 … … , 𝒏𝒉𝒗. Energy in fractions of a quantum cannot be lost or absorbed. This is
known as quantization of energy.
Based on this theory, Planck obtained the following expression for energy density of black body radiation :
8𝜋ℎ𝜈 𝑑𝜈
𝐸 𝜈 𝑑𝜈 = ×
𝑐 4
𝑒 −1
 Above equation accounts for the blackbody radiation curves at all wave lengths obtained at different
temperatures, as shown in above Fig.
Photoelectric Effect
Sir J. J. Thomson, in some of his famous experiments, observed that when light of a certain frequency
strikes the surface of a metal, electrons are ejected from the metal. This phenomenon is known as the
photoelectric effect. A few metals show this effect under the action of visible light but many more show it under
the action of more energetic ultraviolet light.
Cesium, which amongst the alkali metals has the lowest ionization energy, is also the metal from which
electrons are ejected most easily by light. This metal is, therefore, used largely in photoelectric cells.
After making careful studies of photoelectric effect under different conditions, the following
observations were made :
1. For each metal, a certain minimum frequency of incident
light is needed to eject electrons. This is known as threshold
frequency, 𝜈 . A light of smaller frequency than this cannot
eject electrons no matter how long it falls on the metal
surface or how high is its intensity. The threshold frequency
is different for different metals.
2. The kinetic energy of ejected electrons is independent of the
intensity of the incident light but varies linearly with its
frequency. 5
3. The number of ejected electrons from the metal surface depends upon the intensity of the incident radiation.
The greater the intensity, the larger is the number of ejected electrons.
When a photon of light of frequency 𝝊𝒐(threshold frequency) strikes an electron in a metal, it imparts
its entire energy (𝒉𝝊𝒐) to the electron. This energy enables the electron to break away from the atom by
overcoming the attractive influence of the nucleus. Thus, each photon can eject one electron. if the frequency of
the light is less than 𝝊𝒐 , there will be no ejection of electron.
Now suppose the frequency of the light falling on a metal surface is higher than the threshold
frequency 𝝊𝒐 . Let it be 𝝊. When photon of this light strikes a metal surface, some of its energy (which is equal to
the energy binding the electron with the nucleus) is consumed to separate the electron from the metal and the
remaining energy will be imparted to the ejected electron to give it certain velocity v (i.e., kinetic energy =
𝟏
𝟐
𝒎𝒗𝟐 ). Einstein, applying quantum theory, showed that
1
𝒉𝝊 = 𝜙 + m𝑣
2
𝟏
where 𝝓 is the threshold energy (or the work function) of the metal and 𝟐 𝐦𝒗𝟐 is the kinetic energy
imparted to the ejected electron. Evidently
𝜙 = ℎ𝜐
So
1
ℎ𝜐 = ℎ𝜐 + m𝑣 This equation is the Einstein
2 photoelectric equation.
1
m𝑣 = ℎ(𝜐 − 𝜐 ) 6
2
 Heat capacity of free electron gas
Heat capacity : The amount of heat energy required to rise the temp. of a material of mass ‘m’ by 1 °C
/ 1K.
Specific heat capacity : Amount of heat energy required to rise the temp. of one kg of substance by
1K. Unit is J. kg-1K-1
When we applying heat energy from external source on a metal then temp. of metal is raised by
contribution of two parameters
 Lattice contribution
 Electronic contribution
So total specific heat capacity = Lattice contribution + electronic contribution
𝑪𝒗 = 𝑪𝒗𝑳 + 𝑪𝒗𝑬
The value of 𝑪𝒗𝑳 = 𝟑𝑹; (𝑹 = 𝑵𝑨𝒌𝑩)
𝑪𝒗 = 𝟒. 𝟓𝑹 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑡𝑜 𝐶𝑙𝑎𝑠𝑠𝑖𝑐𝑎𝑙 𝑓𝑟𝑒𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 𝑡ℎ𝑒𝑜𝑟𝑦
𝑪𝒗 = ~𝟑. 𝟎𝑹 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑡𝑜 𝑄𝑢𝑎𝑛𝑡𝑢𝑚 𝑓𝑟𝑒𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 𝑡ℎ𝑒𝑜𝑟𝑦

7
 Compton Effect
Arthur Compton found that if monochromatic X-rays (i.e., X-rays having one particular wavelength)
are allowed to fall on carbon or some other light element, the scattered X-rays have wavelengths larger than
the incident rays.
In other words, the scattered X-rays have lower frequency, i.e. lower energy than the incident X-
rays.
Since scattering is caused by electrons, it is evident that some interaction between X-rays and
electrons has taken place and this has resulted in decrease in energy of the former. This decrease in energy or
increase in wavelength of X-rays after scattering from the surface of an object is known as the Compton
effect.
By applying the law of conservation of energy and the law of conservation of momentum and
assuming X-rays to consist of particles (photons), each possessing energy equal to hv; Compton show that

ℎ
𝜆 −𝜆 = (1 − 𝑐𝑜𝑠𝜃)
𝑚 𝑐

Bragg spectrometer
Molybdenum X-ray tube (λ0=0.71 Å) 8
According to this equation , Compton shift should be independent of
the wavelength of incident X-Rays.
If we calculate the energy of incident X-rays
ℎ𝑐
𝐸 = ℎ𝜈 =
𝜆
6.626 × 10 × 3 × 10
= joule
0.71 × 10
6.626 × 10 × 3 × 10
= eV First ionization energy
0.71 × 10 × 1.6 × 10
= 1.7498 × 10 𝑒𝑉 of carbon= 11.26 eV

By applying the law of conservation of energy and momentum and

assuming X-Ray to consist of particle (photons)This has been found to be
experimentally
2ℎ 𝜃
∆𝝀 = 𝑠𝑖𝑛 ∆λ = increases in the wave length (termed as
𝑚𝑐 2
According to this expression Compton shift should be independent of the Compton shift)
wavelength of the incident X-Ray and nature of substance. It only m = rest mass of electron
depend only on scattering angle 𝜽 c = velocity of light
Case-1: scattering angle 𝜃 = 0 ° then ∆𝝀 ⇒ 𝟎 𝜃= angle between incident rays and scattered X-Ray
. ×
Case-2: scattering angle 𝜃 = 90° then ∆𝝀 ⇒ = . × × ×
= 0.02422 × 10 𝑚 = 𝟐. 𝟒𝟐𝒑𝒎
. ×
Case-3: scattering angle 𝜃 = 180° then ∆𝝀 ⇒ ×2 = . × × ×
× 2 = 0.04844 × 10 𝑚=
9
𝟒. 𝟖𝟒𝒑𝒎
 The Bohr's Model of the Atom
Niels Bohr, proposed his model of the atom. He retained Rutherford's model of a very small positively
charged nucleus at the center which contains all the protons and neutrons present in an atom. Bohr also agreed that
the negatively charged electrons are revolving round the nucleus in the same way as the planets are revolving round
the sun. The important postulates of Bohr's theory are :
1. A atom consists of positively charged nucleus responsible for almost entire mass of atom.
2. The electrons in an atom revolve around the nucleus only in certain selected circular orbits. As long as the
electron remains in a particular orbit, it neither loses nor gains energy. This orbit is called stationary orbit or
non-radiating orbit. In other words, the energy of an electron remains constant in a particular orbit. This leads. to
the idea that each orbit is associated with a definite energy; i.e., with a definite whole number of quanta of
energy. The orbits, therefore, are also known as energy levels or energy shells. Bohr gave numbers 1,2,3,4, etc.,
(starting from the nucleus) to these energy levels. These numbers are now termed as principal quantum
numbers. .The various energy levels are also designated by letters K, L, M, N, etc.
3. The energy of an electron cannot change continuously. It changes only abruptly as the electron jumps from-
one energy level to another. The same idea has been expressed, by the statement (that for a change of electronic
energy, the electron has to jump and not to flow from one energy level to another.
4. The angular momentum of an electron moving round the nucleus is quantized. An electron, like any other
body moving in a circular orbit, has an angular momentum given by mvr where m is the mass, v is the linear
velocity of the electron and r is the radius of the orbit. Bohr postulated that the angular momentum of an
electron in an atom can have only definite or discrete values given by the expression
𝒉
Angular momentum (L) = 𝒎𝒗𝒓 = 𝒏 Where n is any integer (1,2, 3, etc.). The integer n is called as
𝟐𝝅
principle quantum number. 10
 Bohr Equation for the Energy of Electron in Hydrogen and Hydrogen-like Atoms.
Working on the above postulate Bohr was able to
calculate the energy of the electron moving in
different orbits round the nucleus in hydrogen or
hydrogen-like atoms such as He+, Li2+, Be3+, B4+
etc. He assumed, as had been suggested by
Rutherford, that the electron remains in its orbit
because the electrostatic force of attraction exerted
by the nucleus is exactly balanced by the
centrifugal force arising from Its circular motion.
According to Bohr quantization condition
𝒉
𝒎𝒗𝒓 = 𝒏
𝒁𝒆 × 𝒆 𝒁𝒆𝟐 𝟐𝝅
= 𝒏𝒉
𝟒𝝅𝜺𝟎𝒓𝟐 𝟒𝝅𝜺𝟎𝒓𝟐 𝒗 =
𝟐𝝅𝒎𝒓
𝑛ℎ 𝑍𝑒
𝑚 =
2𝜋𝑚𝑟 4𝜋𝜀 𝑟
𝒁𝒆𝟐 𝒁𝒆 𝟐
= mv2= The radius rn of nth orbit will be
𝟒𝝅𝜺𝟎𝒓𝟐 𝟒𝝅𝜺𝟎𝒓 (4𝜋𝜀 )𝑛 ℎ
𝑟≡𝑟 = n =1, 2, 3,…….
4𝜋 𝑍𝑚𝑒 11
Radii of stationary orbits are directly proportional to the square of the principle quantum number
 Velocity of electron
𝒏𝒉
We know that 𝒗 =
𝟐𝝅𝒎𝒓
v=c/n * 1/137
𝒏𝒉 𝟏 4𝜋 𝑍𝑚𝑒 𝟏 2𝜋𝑍𝑒
𝒗 ≡ 𝒗𝒏 = × =
𝟐𝝅𝒎 4𝜋𝜀 𝑛 ℎ 4𝜋𝜀 𝒏𝒉
𝟏 2𝜋𝑍𝑒 𝒄
𝒗𝒏 = × c = velocity of light
4𝜋𝜀 𝒄𝒉 𝒏
𝟏 𝟏
The factor ( ) is a constant called as fine structure constant (𝜶) its value to be
𝒄𝒉 𝟏𝟑𝟕
𝒗𝒏 𝜶 𝟏
So for H atom Z=1 and n =1; = =
𝒄 𝟏 𝟏𝟑𝟕
𝟏 th
So velocity of electron in the first orbit is equal to of velocity of light
𝟏𝟑𝟕
Energy of the electron
Suppose Ek and Ep be the kinetic and potential energy in nth orbit
1 𝑍𝑒
𝐸 = 𝐸 + 𝐸 = 𝑚𝑣 −
2 4𝜋𝜀 𝑟
𝟏 𝒁𝒆𝟐
𝐸= − =− (substituting the value of r)
𝟒𝝅𝜺𝟎 𝟐𝒓
1 2𝜋 𝑍2𝑚𝑒
𝐸 =− 2
4𝜋𝜀 𝑛 ℎ n = 1, 2, 3,………..
12
The negative sign show that the electron and nucleus form a bound system, so electron is attracted towards the nucleus

E=-2.178 * 10 TO POWER -18 * Z SQURE /N SQYRE JOULE

 Bohr's Theory and the Origin of Hydrogen Spectrum
Hydrogen atom contains only one electron. But its spectrum consists of a large number of lines.
Bohr given the reason. A given sample of hydrogen contains a very large number of atoms, of the order of several
millions.
Suppose energy is supplied to this sample of the gas. Now different atoms will absorb different amounts
of energy.
According to Bohr, the spectrum arises when the electron in initial stationary orbit of principle quantum
number ni jumps to the final stationary orbit of nf (ni> nf ). So energy difference
1 2𝜋 𝑍2𝑚𝑒 1 2𝜋 𝑍2𝑚𝑒
𝑬 = 𝒉𝝂 = 𝑬𝒊 − 𝑬𝒇 = − − −
4𝜋𝜀 2 𝒏𝟐𝒊 ℎ 4𝜋𝜀 2 𝒏𝟐𝒇 ℎ
1 2𝜋 𝑍2𝑚𝑒 1 2𝜋 𝑍2𝑚𝑒 1 2𝜋 𝑍2𝑚𝑒 1 2𝜋 𝑍2𝑚𝑒 2𝜋 𝑍2𝑚𝑒 1 1
=− + ⇒ − ⇒ −
4𝜋𝜀 2
𝒏𝟐𝒊 ℎ 4𝜋𝜀 2
𝒏𝟐𝒇 ℎ 4𝜋𝜀 2
𝒏𝟐𝒇 ℎ 4𝜋𝜀 2
𝒏𝟐𝒊 ℎ 4𝜋𝜀 2ℎ 𝒏𝒇 𝟐
𝒏𝟐𝒊
1 2𝜋 𝑍2𝑚𝑒 1 1 𝒄 1 2𝜋 𝑍2𝑚𝑒 1 1 𝟏 1 2𝜋 𝑍2𝑚𝑒 1 1
𝝂 = 𝟐
− ⇒ = − ⇒ = −
4𝜋𝜀 2 𝒉𝟑 𝒏𝒇 𝒏𝟐𝒊 𝝀 4𝜋𝜀 2 𝒉𝟑 𝟐
𝒏𝒇 𝒏𝟐𝒊 𝝀 4𝜋𝜀 2 𝒄𝒉𝟑 𝟐
𝒏𝒇 𝒏𝟐𝒊
1 2𝜋 𝑍2𝑚𝑒 1 1
𝝂= 𝟐
−
4𝜋𝜀 2 𝒄𝒉𝟑 𝒏𝒇 𝒏𝟐𝒊
𝟏 𝟏 𝟐𝝅𝟐 𝒎𝒆𝟒
𝝂= = − ⇒ 𝑹𝑯 − For H atom Z=1 and RH =
𝝀 𝒄𝒉𝟑 𝒏𝟐𝒇 𝒏𝟐𝒊 𝟒𝝅𝜺𝟎 𝟐
𝒄𝒉𝟑
RH = Rydberg constant of Hydrogen atom = 13.59 eV
13

1/lambda= RZ SQ {1/N1 SQ -1/N2 SQ} R=1.09 * 10 POWER 7

 For example in Hydrogen atom, may absorb sufficient energy to shift their electrons to the second
energy level only while some others may absorb more energy and may be able to shift their electrons to third or
even to one of the higher energy levels. The electrons then tend to fall back, almost immediately, to one or other of
the lower energy levels.
The various possibilities by which the electrons fall back from various excited state energy levels to
lower energy levels (called electronic transitions), During each transition, energy is released which appears in the
form of radiation of specific frequency and hence of specific wave length.

14
Lyman Series- 𝑛𝑖 = 2,3,4, … … … and 𝑛𝑓 = 1 these lines found in UV region
Balmer Series- 𝑛𝑖 = 3,4,5 … … … and 𝑛𝑓 = 2 these lines found in Visible region
Paschen Series- 𝑛𝑖 = 4,5,6, … . … and 𝑛𝑓 = 3 these lines found Near IR region
Brackett Series- 𝑛𝑖 = 5,6,7, … … and 𝑛𝑓 = 4 these lines found in Near IR region
Pfund Series- 𝑛𝑖 = 6,7,8, … … … . and 𝑛𝑓 = 5 these lines found in far IR region
Humphrey Series- 𝑛𝑖 = 7,8,9, … and 𝑛𝑓 = 6 these lines found in far IR region
This theory was therefore largely accepted.
But after few years the use of high resolving spectroscope reveled that the presence of fine
structures(groups of very close fine lines) in the line spectra of hydrogen atom. So Bohr could not explain
fine structures line spectra of hydrogen atom.
The theory was extended by Sommerfeld by putting the idea of elliptical orbits.
The electron travelling in an elliptical orbit will have its angular
momentum.
The momentum, according to the quantum theory, must also be
quantized and thus can have only a limited number of values
𝒌
given by the factor (where k is an integer known as the
azimuthal quantum number.
It can be shown that n, the principal quantum number, used by
Bohr and k, the azimuthal quantum number used by Sommerfeld,
are related to one another as
15
 According to this theory an electron revolving around a central positively charged nucleus is so
influenced by the nuclear charge that it is set into motion in elliptical orbits with the nucleus situated at one of
the foci (Fig.) Thus, while according to Bohr's theory, electrons move in circular orbits, according to
Sommerfeld's modification, electrons move in elliptical orbits.
There will be a major axis and a minor axis having different lengths. As the orbit broadens, the
lengths of the two axes become closer and they become equal when the orbit becomes circular, as shown in Fig.
Thus, the circular orbit, is only a special case of elliptical orbits.
𝒏 𝒍𝒆𝒏𝒈𝒕𝒉 𝒐𝒇 𝒎𝒂𝒋𝒐𝒓 𝒂𝒙𝒊𝒔
=
𝒌 𝒍𝒆𝒏𝒈𝒕𝒉 𝒐𝒇 𝒎𝒊𝒏𝒐𝒓 𝒂𝒙𝒊𝒔
Thus, for any given value of n (except 1), k can have more than a single value. When k = n, the orbit must be
circular. But, as k becomes smaller, the orbits' become elliptical with greater and greater eccentricity (Fig.). It
may be noted that k cannot be zero because in that case minor axis would be zero which would imply linear
motion of the electron passing through the nucleus.
The number of possible values of k is equal to the principal quantum number n. Thus, if n is 4, k can have four
values; viz., 4, 3, 2 and 1. When n is 1, k can have only one value.
According to Sommerfeld's extension of Bohr theory, also referred to as the Bohr-Sommerfeld model,
the energy depends not only on n, the principal quantum number, but also, on the azimuthal quantum
number, k. Hence, the transition of an electron from one energy level n2 to another energy level n1 will be
different as it would also depend upon the various possible values of k in the two states. This explains the
occurrence of groups of very closely spaced spectral lines observed in the hydrogen line spectrum by using
highly refined spectroscopes. The frequencies of some of these spectral lines were found to be in agreement with
16
the frequencies calculated from the Bohr-Sommerfeld model.
 Objection of Bohr-Sommerfeld’s models
 This model could not explain the spectra of multi-electron containing atom
 De Broglie suggested that electron, like a light, has a dual character, particle as well as wave character.
 In Bohr theory there is no place for the wave character of electron.
 Second objection by Heisenberg's uncertainty principle.
 According to this theory it is impossible to determine simultaneously the exact position and velocity
(momentum) of a minute moving particle like an electron.
 Therefore, the postulate of Bohr theory that electrons revolve round the nucleus in well defined orbits with
will defined velocities is untenable.
Wave-Particle Duality of Electron
Einstein had suggested that light has a dual character; as wave and also as particle.
The Louis de Broglie proposed that matter also has a dual character; as wave and as particle. The name wavicle
was suggested for such a particle.
ℎ
𝜆=
𝑚𝑣
de Broglie equation
𝐸 = 𝑚𝑐 ⇒ ℎ𝜈 = 𝑚𝑐
𝑐
𝜈=
𝜆
𝑐 ℎ 1 𝑚𝑐 ℎ ℎ 𝒉
ℎ = 𝑚𝑐 ⇒ = 𝑚𝑐 ⇒ = ⇒𝜆= = =
𝜆 𝜆 𝜆 ℎ 𝑚𝑐 𝑚𝑣 𝒑
17
p = linear momentum of the particle
 Calculate the de Broglie wave length of electron moving with a velocity of l.20×l05ms-1. Mass of
electron = 9.l×10-31 kg. The value of plank constant (h) = 6.626×10-34 J.s.

ℎ
𝜆=
𝑚𝑣
𝟔. 𝟔𝟐𝟔 × 𝟏𝟎 𝟑𝟒
𝜆=
𝟗. 𝟏 × 𝟏𝟎 𝟑𝟏 × 𝟏. 𝟐𝟎 × 𝟏𝟎𝟓
𝜆 = 𝟔. 𝟎𝟔𝟖 × 𝟏𝟎 𝟗 𝒎 = 𝟔𝟎. 𝟔𝟖 Å

Calculate the de Broglie wave length of a body of mass 1.0 kg moving with a velocity of 2000 ms-1
ℎ
𝜆=
𝑚𝑣
𝟔. 𝟔𝟐𝟔 × 𝟏𝟎 𝟑𝟒
𝜆=
𝟏. 𝟎 × 𝟐𝟎𝟎𝟎
𝜆 = 𝟑. 𝟑𝟏𝟑 × 𝟏𝟎 𝟑𝟕 𝒎 = 𝟑. 𝟑𝟏𝟑 × 𝟏𝟎 𝟐𝟕 Å

It may be noted that the above wave length is too small to be measured by any conceivable technique.

18
 Distinction between matter waves and electromagnetic waves
It should be carefully noted that matter waves are distinctly different from electromagnetic waves.
 The speed of matter waves is much less than electromagnetic waves (light).
 These matter waves cannot be radiated in empty space. They are certainly not emitted by the particle
under consideration; they are simply associated with it.
 The wave lengths of matter waves are generally very small as compared to the wave lengths of
electromagnetic waves.
Heisenberg's Uncertainty Principle
 It states that it is not possible to determine precisely both the position and the momentum (velocity) of a
small moving particle.
 Consider a photon incident on a particle. If the particle is of
reasonable size, its position or velocity will not be altered by the
impact of light photons. Hence it will be possible to know exactly
both the position and velocity of the particle.
 But, this cannot be so when the particle is extremely minute, such
as an electron.
 It will suffer a change in its velocity and path due to the impact of
even a single photon of light used to observe it.
 The path and velocity of an electron, after the impact of light
photons, maybe quite different from the original path and velocity. 19
For an electron moving in 𝒙 − 𝒅𝒊𝒓𝒆𝒄𝒕𝒊𝒐𝒏, the Heisenberg uncertainty principle is expressed mathematically as
𝒉
∆𝒙 ∆𝒑𝒙 ≥
𝟒𝝅
Where ∆𝒙 is uncertainty with regards to position and ∆𝒑𝒙 is uncertainty with regards to momentum of
the electron.
 if ∆𝒙 is very small, i.e., the position of a particle is known more or less exactly, ∆𝒑𝒙 would be large, i.e.
uncertainty with regard to momentum will be large.
 Similarly, if an attempt is made to measure exactly the momentum of the particle, the uncertainty with regard
to position will become large.
 Hence, uncertainty arises due to the wave nature of the electron.
A microscope using suitable photons is employed to locate an electron in an atom within a distance of
0·1 Å. What is the uncertainty involved in the measurement of its velocity ? Mass of electron = 9.l×10-31 kg.
The value of plank constant (h) = 6.626×10-34 J.s.
𝒉
∆𝒙 ∆𝒑𝒙 ≥
𝟒𝝅
𝒉
∆𝒙 𝒎 × ∆𝒗 ≥
𝟒𝝅
𝟑𝟒
𝟔. 𝟔𝟐𝟔 × 𝟏𝟎
𝟎. 𝟏 × 𝟏𝟎 𝟏𝟎 × 𝟗. 𝟏 × 𝟏𝟎 𝟑𝟏 × ∆𝒗 =
𝟒 × 𝟑. 𝟏𝟒
𝟑𝟒
𝟔. 𝟔𝟐𝟔 × 𝟏𝟎
∆𝒗 = 𝟏𝟎 𝟑𝟏
= 𝟎. 𝟓𝟕𝟗 × 𝟏𝟎𝟕 𝒎𝒔 𝟏
𝟒 × 𝟑. 𝟏𝟒 × 𝟎. 𝟏 × 𝟏𝟎 × 𝟗. 𝟏 × 𝟏𝟎
20
(J=kg.m .s )
2 -2
 A cricket ball weighing 100 g is to be located within 0·1 Å. What is the uncertainty in its velocity?
Comment on your result. The value of plank constant (h) = 6.626×10-34 J.s.
𝒉
∆𝒙 ∆𝒑𝒙 ≥
𝟒𝝅
𝒉
∆𝒙 𝒎 × ∆𝒗 ≥
𝟒𝝅
𝟏𝟎
𝟔. 𝟔𝟐𝟔 × 𝟏𝟎 𝟑𝟒
𝟎. 𝟏 × 𝟏𝟎 × 𝟎. 𝟏 × ∆𝒗 =
𝟒 × 𝟑. 𝟏𝟒
𝟑𝟒
𝟔. 𝟔𝟐𝟔 × 𝟏𝟎
∆𝒗 = 𝟏𝟎
= 𝟎. 𝟓𝟐𝟕 × 𝟏𝟎 𝟐𝟐 𝒎𝒔 𝟏
𝟒 × 𝟑. 𝟏𝟒 × 𝟎. 𝟏 × 𝟏𝟎 × 𝟎. 𝟏
Comparing this value with the typical velocity of a cricket ball, we find that this uncertainty in
velocity is completely negligible.
This means that we can disregard the uncertainty principle for the motion of macroscopic bodies.
We can thus say that for such cases both the position and velocity can be determined to a reasonable degree of
precision.

21
 The concept of an electron following a definite orbit means its position and velocity are known exactly.
So its position and velocity are known exactly, must therefore be replaced by the probability of finding
of an electron in a particular position or in a particular volume of space.
Schrödinger wave equation provides a satisfactory description of an atom in these term.
The Schrödinger wave equation is a mathematical expression describing the energy and position of the
electron in space and time, taking into account the matter wave nature of the electron inside an atom.
The wave equation are called wave functions and its symbol (𝝍).
The probability of finding an electron at a point in the space whose coordinate are x, y, and z axis is 𝝍 2 (x, y, z)
It is based on three considerations.
 Classical plane wave equation
 Broglie’s hypothesis of matter-wave
 Conservation of energy
 Erwin Schrodinger based on dual nature of electron. Electron is described in three dimensional wave in the
electric field of a positively charged nucleus. The probability of finding electron at any point around the
nucleus can be determined by the help of Schrodinger wave equation.
 In Schrodinger wave model, the discrete energy level or orbits proposed by Bohr are replaced by
mathematical function (𝝍), which are related to the probability of finding electrons at various places around
the nucleus.
 For standing wave (such as a vibrating string) of wavelength 𝝀, whose amplitude at any point along x axis
may be described by function 𝒇(𝒙). It can be shown that
22
 𝜕 𝑓(𝑥) 4𝜋
=− 𝑓(𝑥)
𝜕𝑥 𝜆
If an electron is considered as a wave which moves in only one dimension
𝜕 𝝍 4𝜋
=− 𝝍
𝜕𝑥 𝜆
but electron may moves in three dimension directions 𝒙, 𝒚, and 𝒛 so this equation becomes
𝜕 𝝍 𝜕 𝝍 𝜕 𝝍 4𝜋
+ + =− 𝝍
𝜕𝑥 𝜕𝑦 𝜕𝑦 𝜆
Using a symbol 𝜵 instead of above these three partial differential equation
4𝜋
𝛻 𝝍=− 𝝍
𝜆
𝜵𝟐 =laplacian mathematical operator
According to de Broglie
ℎ
𝝀=
𝒎𝒗
Where h Planck’s constant, m is the mass of electron, and v is the velocity of electron
4𝜋 𝒎𝟐 𝒗𝟐
𝛻 𝝍=− 𝝍
𝒉𝟐
4𝜋 𝒎𝟐 𝒗𝟐
𝛻 𝝍+ 𝝍=0
𝒉𝟐
But total energy of the system E is made up with kinetic energy (𝑲) and potential energy(𝑽)
23
𝐸 =𝐾+𝑉 ⇒𝑲=𝑬−𝑽
 1
𝐾 = 𝑚𝑣
2
So
𝑚𝑣 = 𝐸 − 𝑉
2
𝑣 = 𝐸−𝑉
𝑚
So well known form of Schrödinger wave equation
4𝜋 𝑚 2 8𝜋 𝑚
𝛻 𝜓+ 𝐸−𝑉 𝜓 =0⇒𝛻 𝜓+ 𝐸−𝑉 𝜓 =0
ℎ 𝑚 ℎ
2𝑚(2𝜋) 2𝑚 ℏ
𝛻 𝜓+ 𝐸−𝑉 𝜓 =0⇒𝛻 𝜓+ 𝐸−𝑉 𝜓 =0⇒ 𝛻 𝜓+ 𝐸−𝑉 𝜓 =0
ℎ ℏ 2𝑚
ℏ ℏ
− 𝛻 𝜓 − 𝐸𝜓 + 𝑉𝜓 = 0 ⇒ − 𝛻 𝜓 + 𝑉𝜓 = 𝐸𝜓
2𝑚 2𝑚
ℏ
− 𝛻 + 𝑉 𝜓 = 𝐸𝜓
2𝑚
𝐻𝜓 = 𝐸𝜓
ℏ
The Hamiltonian operator (𝐻) consist two parts Kinetic energy part − 𝛻 and the electrostatic
potential part (V).

ℎ 24
ℏ=
2𝜋
 Acceptable solutions to the wave equation, that is solution which are physically possible, must have
certain properties
1. 𝝍 must be continuous
2. 𝝍 must be finite
3. 𝝍 must be singled valued
4. The probability of finding the electron over all the space from +∞ 𝒕𝒐 − ∞ must be equal to one.
The probability of finding an electron at a point x, y, z is 𝝍𝟐, so
+
𝜓 𝑑𝑥 𝑑𝑦 𝑑𝑧 = 1

Several wave functions called 𝝍𝟏, 𝝍𝟐, 𝝍𝟑, 𝝍𝟒, 𝝍𝟓……………. 𝝍n will follow the above equation condition.
Each wave function have energy 𝑬𝟏, 𝑬𝟐, 𝑬𝟑, 𝑬𝟒, 𝑬𝟓, … … … . . 𝑬𝒏
And each of these function (𝝍𝟏, 𝝍𝟐, 𝝍𝟑, 𝝍𝟒, 𝝍𝟓……………. 𝝍n ) called as orbital/orbits.
In hydrogen atom, the single electron normally occupies the lowest energy levels E1. so this energy level is
called as ground state and its corresponding wave function 𝝍𝟏 whose described the orbital/orbits.
That is the volume in the space where there is high probability of finding the electron.
The number of solutions to the wave equation which are acceptable, and each orbital may be described
uniquely by a set of three quantum numbers, n, l and m. (These are the same quantum numbers - principal,
subsidiary and magnetic - as were used in the Bohr theory).
The subsidiary quantum number l describes the shape of the orbital occupied by the electron. l may have
25
values 0, 1, 2 or 3.
 When l = 0, the orbital is spherical and is called an s orbital;
In the first group of solution, The value of the wave function 𝝍, and the
probability of finding the electron 𝝍2 , depends only on the distance r from the
nucleus, and is the same in all directions
𝝍 = 𝒇(𝒓)
This leads to a spherical orbital, and occurs when the subsidiary
quantum number l is zero. These are called s orbitals. When l = 0, the magnetic
quantum number m = 0, so there is only one such orbital for each value of n.

when l = l, the orbital is dumb-bell shaped and is called a p orbital;

26
 In the second group of solutions to the wave equation, 𝝍 depends both on the distance from the
nucleus, and on the one direction in space (x, y or z).
Orbitals of this kind occur when the subsidiary quantum number l = 1. These are called p orbitals
and there are three possible values 𝝍 the magnetic quantum number (m = -1, 0 and +1). There are
therefore three orbitals which are identical in energy, shape and size, which differ only in their direction
in space. These three solutions to the wave equation may be written
𝝍𝒙 = 𝑓 𝑟 . 𝑓(𝑥)
𝝍𝒚 = 𝑓 𝑟 . 𝑓(𝑦)
𝝍𝒛 = 𝑓 𝑟 . 𝑓(𝑧)

Orbitals that are identical in energy are termed degenerate, and thus three degenerate p orbitals
occur for each of the values of n = 2, 3, 4 ...
27
 The third group of solutions to the wave equation 𝝍 depend on the distance from the nucleus r and
also on two directions in space, for example
𝝍 = 𝒇(𝒓). 𝒇(𝒙). 𝒇(𝒚)
when l = 2, the orbital is double dumb-bell shaped and is called a d orbital;
there are five solutions corresponding tom = -2, -1, 0, + 1 and +2, and these are all equal in energy. Thus five
degenerate d orbitals occur for each of the values of n = 3, 4, 5 ....

Note: The + and ̶ signs refer to symmetry, not a charge

28
 The forth group of solutions to the wave equation 𝝍 depend on the distance from the nucleus r and
also on three directions in space, for example 𝝍 = 𝒇(𝒓). 𝒇(𝒙). 𝒇(𝒚).𝒇(𝒛)
when l = 3 a more complicated f orbital is formed. There are seven values of m : -3, -2, -l, 0, +l, +2
and +3 and seven degenerate f orbitals are formed when n = 4, 5, 6 ....

The letters s, p, d and f come from the spectroscopic terms sharp, principal, diffuse and
fundamental, which were used to describe the lines in the atomic spectra. 29
 RADIAL AND ANGULAR FUNCTIONS
The Schrodinger equation can be solved completely for the hydrogen atom, and for related ions
which have only one electron such as He+ and Li2+. For other atoms only approximate solutions can be
obtained.
For most calculations, it is simpler to solve the wave equation if the cartesian coordinates x, y and
z are converted into polar coordinates r, 𝜽 and 𝝓.

Radial wave function- principle quantum number and azimuthal quantum number (n, l) give information
about distribution of electron from radius r
𝑹 𝒓 = 𝑹𝒏. 𝒍(𝒓)
Angular wave function -azimuthal quantum number and magnetic quantum number(l, m) give information
about shape of electron cloud / orbitals and depend on l and m
The angular wave function
A 𝜽, 𝝓
So complete wave function
𝝍 𝒓, 𝜽, 𝝓 = 𝑹 𝒓 . 𝑨(𝜽,𝝓)
The complete wave function represents an orbital in which the radial part give information about
size and angular part give shape.
Angular wave function does not on principal quantum number. It means that shape of all s
orbital are same. Similarly for p, d, f…….
30
It only depends on the direction given by 𝜃 and 𝜙
 The coordinates of the point A measured from the origin are x, y and z in cartesian coordinates, and
r, 𝜽 and 𝝓. in polar coordinates. It can be seen that the two sets of coordinates are related by the following
expressions.

𝑧 = 𝑟. 𝑐𝑜𝑠𝜃
𝑦 = 𝑟. 𝑠𝑖𝑛𝜃. 𝑠𝑖𝑛𝜙
𝑥 = 𝑟. 𝑠𝑖𝑛𝜃. 𝑐𝑜𝑠𝜙

The relationship between cartesian and polar coordinates

The Schrödinger equation is usually written as

8𝜋 𝑚
𝛻 𝜓+ 𝐸−𝑉 𝜓=0
ℎ
𝜕 𝝍 𝜕 𝝍 𝜕 𝝍
𝛻 𝜓= + +
𝜕𝑥 𝜕𝑦 𝜕𝑦
Changing to polar coordinates, 𝛻 𝜓 becomes
1 𝜕 2 𝜕𝝍 1 𝜕 𝝍 1 𝜕 𝜕𝝍
𝛻 𝜓= . 𝑟 + . + . 𝑠𝑖𝑛𝜃
𝑟 𝜕𝑟 𝜕𝑟 𝑟 𝑠𝑖𝑛2𝜃 𝜕𝜙 𝑟 𝑠𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 31
 The solution of this is of the form
𝝍 = 𝑹 𝒓 . 𝚯 𝜽 . 𝚽(𝝓)
 R(r) is a function that depends on the distance from the nucleus, which in turn depends on the
quantum numbers n and l
 𝚯 𝜽 is a function of 𝜽; which depends on the quantum numbers l and m
 𝚽(𝝓) is a function of 𝝓; which depends only on the quantum number m
𝝍𝒏, 𝒍, 𝒎 = 𝑹 𝒓 𝒏, 𝒍. 𝑨 𝜽, 𝝓 𝒍, 𝒎

 The radial function R has no physical

meaning,
 but R2 gives the probability of finding the
electron in a small volume dv near the point
at which R is measured. For a given value
of r the number of small volumes is 4πr2dr,
so the probability of the electron being at a
distance r from the nucleus is 4πr2drR2.
This is called the radial distribution
function.
Radial distribution function for hydrogen
plotted against r are shown in given figure Radial distribution functions for various orbitals in the hydrogen atom
32
 𝜓 .. = 𝑅 . 𝑟 × 𝐴. 𝜃, ∅

Characteristics of Radial distribution

function
 The diagram show that the probability is
zero at the nucleus (as r = 0)
 By examining the plots for 1s, 2s and 3s
that the most probable distance
increases markedly as the principal
quantum number increases.
So, All the s orbitals except the first one (1s) have a shell-like structure, rather like an onion,
consisting of concentric layers of electron density.
In case of Hydrogen atom in its ground state (when electron is in 1s state ) the radius of
33
maximum probability is 0.529Å.
 By comparing the plots for 2s and 2p, or 3s, 3p and
3d it can be seen that the most probable radius
decreases slightly as the subsidiary quantum
number increases

Similarly, all but the first p orbitals (2p) and the first d orbitals (3d) have a shell structure.
Consequently, there are two types of nodes. Radial nodes occur where the radial component of
the wave function passes through zero and
angular nodes occur where the angular component of the wave function passes through zero.
The numbers of both types of node increase with increasing energy and are related to the quantum
numbers n and l.
34
 Radial Nodes/ spherical nodes : Radial nodes/ occur when the wave function for
the electron is zero on the spherical surface of a particular radius.
 The plot of the probability of 3s wave function. The two radial nodes are appears.
 Number of radial or spherical nodes = 𝒏 − 𝒍 − 𝟏
 Number of peaks in radial distribution curve = 𝒏 − 𝒍

 Number of radial or spherical nodes in 2s = 𝟐 − 𝟎 − 𝟏 = 𝟏

 Number of peaks in radial distribution curve of 2s = 𝟐 − 𝟎 = 𝟐
How many radial nodes do 3p, 3d, and 4f orbitals have?
Radial nodes Number of peaks
3p = 𝟑 − 𝟏 − 𝟏=1 3p = 𝟑 − 𝟏=2
3d = 𝟑 − 𝟐 − 𝟏=0 3d = 𝟑 − 𝟐=1
4f = 𝟒 − 𝟑 − 𝟏=0 4f = 𝟒 − 𝟑=1

35
Angular wave function:
 The angular function A depends only on the
direction, and is independent of the distance
from the nucleus (r).
 Thus A2 is the probability of finding an
electron at a given direction 𝜽, 𝝓 at any
distance from the nucleus to infinity.
 The angular functions A are plotted as polar
diagrams in given Figure. It must be
emphasized that these polar diagrams do not
represent the total wave function 𝝍,
 but only the angular part of the wave
function. (The total wave function is made
up from contributions from both the radial
and the angular functions.)
Angular Nodes/planar nodes/Nodal planes:
Angular Nodes occur when wave function for the electron is zero along
direction specified angle.
The plot of the probability of 2p wave function. The angular nodal
plan/surface make 90o angle with z axis. 36
Number of Angular Nodes of 2p = l =1 Angular Nodes of 3d = l =2
The three dimensional view of 2p orbital The three dimensional view of 3d orbital

Angular Nodes = l =3
The three dimensional view of 4f orbital

Total number of nodes of any orbital

= 𝑁𝑜. 𝑜𝑓 𝑅𝑎𝑑𝑖𝑎𝑙 𝑛𝑜𝑑𝑒𝑠 + 𝑁𝑜. 𝑜𝑓 𝐴𝑛𝑔𝑢𝑙𝑎𝑟 𝑛𝑜𝑑𝑒𝑠
= 𝒏−𝒍−𝟏+𝒍
=𝒏−𝟏

37
The atom is built up by filling electrons in various orbitals according to the certain rules likes Aufbau principle,
Pauli exclusion principle and Hund’s rule of maximum spin multiplicity.
Aufbau principle: this principle state that electrons are added one by one to the various orbitals in order of their
increasing energy starting with the orbital of lowest energy of various atomic orbitals is
The sequence of atomic orbitals shown based on (𝒏 + 𝒍) rule
 In neutral isolated atom have lower (𝒏 + 𝒍) value will have
lower energy
 If two different types of orbitals have same (𝒏 + 𝒍) value, so
orbitals with lower value of n has lower energy.

Gerade(g) and ungerade(u) orbitals

s g p u
d g f u

38
 PAULI’s EXCLUSION PRINCIPLE
According to this principle no two electrons in one atom can have all four quantum numbers the same.
 No more than two electrons can occupy the same orbital and
 Two electrons in the same orbital must have opposite spins

 This means if one electron is assigned as a spin up (+1/2) electron, the other electron must be spin-
down (−1/2) electron.
Hund’s rule
When atoms are in their ground state, the electrons occupy the lowest possible energy levels.
This rule deals with the filling of electrons in the orbitals having equal energy also known as
degenerate orbitals.
According to this rule “Degenerate orbitals must be singly occupied before the spin pairing
starts.”
Spin multiplicity – In quantum chemistry is used to express the number of possible orientations of spin
angular momenta
𝟐𝑺 + 𝟏 where 𝑺 is spin angular momentum
 When all electrons are paired then 𝑺 = 𝟎 and spin multiplicity will be =𝟏; singlet
 If atom has one unpaired electron then 𝑺 = 𝟏/𝟐 and spin multiplicity will be =𝟐; doublet
 If atom have two unpaired electrons then 𝑺 = 𝟏 and spin multiplicity will be =𝟑; triplet
 So when atoms/molecules with odd multiplicity are usually more stable than those with even
39
multiplicity
 Effective Nuclear charge and slater’s rule
In multi-electron atom, each electron experiences less than the actual nuclear charge owing to
shielding or screening by the other electrons.
Slater’s rule provides numerical value for the effective nuclear charge.
For each electron in an atom, Slater’s rule provides numerical value for screening constant denoted by
S which co-relate with effective and actual charges as
𝒁 𝒆𝒇𝒇. = 𝒁 − 𝒔
Z= actual nuclear charge
Zeff. is effective nuclear charge
Firstly the electrons are arranged into sequence group in order of increasing principal quantum number n and
for equal n in order of increasing azimuthal quantum number l, expect that s- and p- orbitals are kept together-
[𝟏𝒔], [𝟐𝒔, 𝟐𝒑], [𝟑𝒔, 𝟑𝒑][𝟑𝒅], [𝟒𝒔, 𝟒𝒑], [𝟒𝒅], [𝟒𝒇], [𝟓𝒔, 𝟓𝒑], [𝟓𝒅], [𝟓𝒇]
Each group is given a different shielding constant which depends upon the number and types of
electrons in those groups preceding it. The shielding constant for each group is formed as the sum of the
following contribution-
1. An amount of 0.35 from each other electron within the same group expect for 1s group, were the other
electron contribute only 0.30.
2. If the groups is of (s, p) types, an amount of 0.85 from each electron with principal quantum number n-1
and an amount of 1.00 for each electron with even smaller principal number.
3. Group is d or f type, an amount of 1.00 for each electron inside it. This include
(i) electrons with smaller principal quantum number n and
40
(ii) electron with an equal principal quantum number and a smaller azimuthal quantum number l
 group Other Electron in group(s) with Electron in Electron in all
electron principal quantum group(s) with group(s) with
in same number n and azimuthal principal quantum principal quantum
group quantum number < 𝒍 number 𝒏 − 𝟏 number < 𝒏 − 𝟏
1𝑠 0.30 N/A N/A N/A
𝑛𝑠, 𝑛𝑝 0.35 N/A 0.85 1.00
𝑛𝑑 𝑜𝑟 𝑛𝑓 0.35 1.00 1.00 1.00
What is the effective nuclear charge felt by 1s electron of helium atom?
The electronic configuration of helium atom is 1s2
There is one more 1s electron, a part from the electron for which Zeff is to be calculated.
The screening constant. s =1x 0·30 =0·30
Hence. Zeff felt by 1s electron of helium atom =2 - 0·30=1.70
What is the effective nuclear charge felt by a 2p electron of a nitrogen atom? What will be the effective nuclear
charge felt by its 1s electron?
Zeff for 2p electron
Electronic configuration of N atom is 1s2 2s2 2p3
There are four other electrons in (2s, 2p) group.
Screening constant S for 2p electron = 4x0.35 + 2x0.85 = 1.40 + 1·70 = 3·10
Zeff felt by 2p electron = Z - S = 7 - 3. 10 = 3·90
Zeff. for 1s electron :
Zeff felt by 1s electron = Z- S = 7- 1x 0·30 = 6.70 41
 Particle in a One-Dimensional Box
This is the simplest quantum mechanical problem which represents
translational motion. Here a particle of mass m is confined to move in a one-
dimensional box of width a, having infinitely high walls (given fig.). It is
assumed, for the sake of simplicity, that the potential energy of the particle is
zero everywhere inside the box, that is
𝑉 𝑥 = 0 −−−− −(𝟏)
Thus, inside the box the Schrödinger equation. viz. ,
ℏ 𝑑
− + 𝑉(𝑥) 𝜓 = 𝐸𝜓 𝑥 −−−− −(𝟐)
2𝑚 𝑑𝑥

ℏ 𝑑 𝜓
− = 𝐸𝜓(𝑥) −−−− −(𝟑)
2𝑚 𝑑𝑥
Our problem is to solve this equation for energy E and the wave function 𝝍 𝒙
Mathematically eq.(3) written as
𝑑 𝜓 2𝑚
= −𝐸𝜓(𝑥) −−−− −(𝟒)
𝑑𝑥 ℏ
𝑑 𝜓 2𝑚𝐸
+ 𝜓 = 0 −−−− −(𝟓)
𝑑𝑥 ℏ
𝑑 𝜓
+ 𝑘 𝜓 = 0 −−−− −(𝟔)
𝑑𝑥 42
k = ℏ is constant independent on x
Eq. (6) is an ordinary second-order differential equation which has solution of the form
𝝍 = 𝑨 𝒄𝒐𝒔 𝒌𝒙 + 𝑩 𝒔𝒊𝒏 𝒌𝒙 −−−− −(𝟕)
where A and B are constants
Before we proceed further it should be pointed out that out side the box where 𝑽(𝒙) = ∞, the
Schrödinger equation (2) will be
ℏ 𝑑
− + ∞ 𝜓 = 𝐸𝜓 𝑥 −−−− −(𝟖)
2𝑚 𝑑𝑥
𝑑 𝜓 2𝑚
+ 𝐸 − ∞ 𝜓 = 0 −−−− −(𝟗)
𝑑𝑥 ℏ
 This equation is satisfied if 𝝍 is zero everywhere outside the box.
 This is another way of saying that the particle cannot be found outside the box; it is confined within the
box.
 This implies that 𝝍 must be zero at the walls of the box, i.e., at x = 0 and at x=a. Since the postulate of
quantum mechanics requires that 𝝍 must be a continuous function of x,
 we are forced to conclude that in Eq. (7), A must be zero. Thus, the solution of Eq. (6) is of the form
𝜓 = 𝐵 𝑠𝑖𝑛 𝑘𝑥 −−−− −(𝟏𝟎)
𝝍 = 𝟎 𝑎𝑡 𝒙 = 𝟎 𝑎𝑛𝑑 𝒙 = 𝒂 we have
𝐵 𝑠𝑖𝑛 𝑘𝑎 = 0 −−−− −(𝟏𝟏)
43
 𝒏𝝅
𝒔𝒊𝒏 𝒌𝒂 = 𝟎 𝑜𝑟 𝒌𝒂 = 𝒏𝝅 so 𝒌 =
𝒂

where n = 0,1,2,3,4,5…………………..
So allowed solutions of equation (6)
𝒏𝝅𝒙
𝝍 = 𝝍𝒏 = 𝑩 𝒔𝒊𝒏 𝒂
𝒌𝒙 (𝑤h𝑒𝑟𝑒 n = 0,1,2,3,4,5…………………..) −−−− −(𝟏𝟐)

Notice that the 𝒏 = 𝟎 value of the quantum number, though allowed, is not acceptable since it implies
that the wave function 𝝍 is zero everywhere in side the box.
This is not correct since the particle is taken to be inside the box to begin with from. Eqs;(6) and (11),
we have
2𝑚𝐸 𝑛 𝜋
= −−−− −(𝟏𝟑)
ℏ 𝑎
ℏ h h
𝐸≡𝐸 = = (𝑤h𝑒𝑟𝑒 n=1,2,3,4,5………and ℏ= ) −−−− −(𝟏𝟒)
 ℏ is known as is called reduced plank’s constant and also Dirac's constant
 This equation (14) gives the expression for energy of particle in a one dimensional box.
 Since energy depends upon the quantum number n, the energy levels are quantized,
 Let us determine the coefficient B in the wave function given by Eq. (12) This can be done by
normalizing the wave function 44
Normalization of 𝝍
Since the total probability of finding the particle within the box is 1,
∫ 𝝍 𝑑𝑥 = 1 (Born’s interpretation of wave function) −−−− −(𝟏𝟓)
𝑩 𝒔𝒊𝒏
∫ 𝑑𝑥 = 1 (using from eq.(12) −−−− −(𝟏𝟔)
or
𝒔𝒊𝒏
𝐵 ∫ 𝑑𝑥 = 1 −−−− −(𝟏𝟕)
Since 𝑠𝑖𝑛 𝜃 = (1 − cos 2𝜃) hence from Eqs. (15) and (17), we have
1 1 2𝑛𝜋𝑥
𝝍 𝑑𝑥 = 𝐵 𝑑𝑥 − 𝑐𝑜𝑠 𝑑𝑥 −−−− −(𝟏𝟖)
2 2 𝑎
𝑎
𝐵 − 0 = 1 −−−− −(𝟏𝟗)
2
2
𝑩= −−−− −(𝟐𝟎)
𝑎
Thus, the normalized wave functions for the particle are
𝜓 𝑥 = sin 𝑤h𝑒𝑟𝑒 n=1,2,3,4,5…. −−−− −(𝟐𝟏)

45
1. Write out the electronic configuration of the element in the following order and groupings:
[𝟏𝒔], [𝟐𝒔, 𝟐𝒑], [𝟑𝒔, 𝟑𝒑][𝟑𝒅], [𝟒𝒔, 𝟒𝒑], [𝟒𝒅], [𝟒𝒇], [𝟓𝒔, 𝟓𝒑], [𝟓𝒅], [𝟓𝒇]
2. Electrons in any group to right of the (ns, np) group contribute nothing to the shielding constant.
3. All of the other electrons in the (ns, np) group, shield the valance electron to an extant of 0.35 each.
4. All electrons in the (n-1) shell shield to an extant 0.85 each
5. All electrons in the (n-2) or lower shell shield to an extant 1.00 each
When the electron being shielded in nd, or nf group, Rule (2) and (3) are the same (4) and (5) become
6. All electrons in the groups lying to the left of the nd and nf group contribute 1.00 each
 Ex. Consider the valance electron in the atom 7N=1s22s22p3
Grouping the orbitals give (1s)2(2s,2p)5
S=(2x 0.85) + (4x0.35)=3.10
Z*=Z-S= 7-3.10=3.9
 Ex. Consider the valance(4s) electron in the atom 30Zn. The electronic configuration; 30Zn =
1s22s22p63s23p64s23d10
Grouping the orbitals give (1s)2(2s,2p)8(3s,3p)8 (3d)104s2
S=(1x 0.35) + (18 x 0.85) + (10 x 1.0) =25.65
46
Z*=Z-S= 30-25.65= 4.35
 Ex. Consider the valance(3d) electron in the atom 30Zn. The electronic configuration; 30Zn=
1s22s22p63s23p64s23d10
Grouping the orbitals give (1s)2(2s,2p)8(3s,3p)8 (3d)104s2
S=(9 x 0.35) + (18 x 1.0) = 21.15
Z*=Z-S= 30 -21.15= 8.85
 Calculate the effective nuclear charge felt by a 3d electron of the chromium = 24).
The grouping of electrons in Cr atom according to Slater’ rules is (1s2) (2s22p6) (3s23p6) (3d5) (4s1)
There will be no contribution from 4s electron.
There are 4 other 3d electrons.
So Zeff. Felt by the 3d electron of Cr atom = 24- (0.35x4 + l.0x18)=4.60
 The electron is revolving around the nucleus in a circular orbit. So how many resolution it can make in
one second?
Let the velocity of electron be (𝑣) 𝑚/𝑠
the distance travel by electron for one complete revolution is 𝟐𝝅𝒓.
thus, the number of revolution per second is 𝒗/𝟐𝝅𝒓
Physical significance of 𝝍 𝒂𝒏𝒅𝝍𝟐
 The wave function 𝝍 represents the amplitude of the electron wave.
 The amplitude 𝝍 is thus a function of space coordinates and time.
 𝝍𝟐 refers to the probability density of finding electrons.
 So, for single particle, the square of the wave function 𝝍𝟐 at any point is proportional to the probability
of finding the particle at that point. 47
 If 𝝍𝟐is maximum tan probability of finding electron is maximum around the nucleus and place were the
probability of finding electron is maximum is called atomic orbital.
 Electronic configuration of any element
𝒙
𝒏𝒍

Factors Responsible for the Extra Stability of Half-filled and Completely Filled Sub-shells
 Symmetrical distribution: It is well known fact that symmetry leads to stability. Thus the electronic
configuration in which all the orbitals of the same subshell are either completely filled or are exactly half
filled are more stable because of Symmetrical distribution of electrons .
 Exchange energy : The electrons with parallel spins present in the degenerate orbitals tend to exchange
their position. The energy released during this exchange is called Exchange Energy. The number of
exchanges that can take place is maximum when the degenerate orbitals are exactly half-filled or
completely filled. As a result, the exchange energy is maximum and so is the stability.
 Ground state electronic configuration of nitrogen atom can be represented by
(a) (b)

(c) (d)

Only the configuration (a) and (d) follow Hund 's rule.

48
 Which is the correct outermost shell configuration of chromium
(a) (b)

(c) (d)

 The quantum numbers of most energetic electron in Ne atom when it is in first exited state
(a) 2, 1, 0,±1/2 (b) 3, 1, 1,±1/2
(c) 3, 0, 0,±1/2 (d) 3, 1, 0,±1/2
 The electronic configuration n of an element is 1s2, 2s2,2p6, 3s2,3p6,3d10,4s1. This represents it
(a) Exited State (b) Ground State
(c) Cationic form (d) Anionic form
 The energy of an electron in a hydrogenic ion depend on
(a) n, l, m only (b) n, l only
(c) n only (d) n, l, m, s only
49