ATOMS

MODELS OF ATOM
First model of atom - J. J. Thomson’s model of atom.
 According to this model, the positive charge of the atom is uniformly distributed
throughout the volume of the atom and the negatively charged electrons are
embedded in it like seeds in a watermelon.
 This model was picturesquely called plum pudding model of the atom
Alpha-Particle Scattering and Rutherford’s Nuclear Model of Atom.
Geiger-Marsden Alpha-Particle Scattering Experiment.
Experimental setup and experiment

 Fine beam of 5.5 MeV α-particles emitted from a 214 83Bi radioactive source is
directed at a thin metal foil made of gold of thickness 2.1 × 10–7 m.
 The scattered alpha-particles were observed through a rotatable detector consisting
of zinc sulphide screen and a microscope.
 The scattered alpha-particles on striking the screen produced brief light flashes or
scintillations.
 These flashes may be viewed through a microscope and the distribution of the
number of scattered particles may be studied as a function of angle of scattering.
Observations and predictions.
 A typical graph of the total number of α-particles scattered at different angles, in a
given interval of time, is shown below.
 Many of the α-particles pass through the foil. It means that they do not suffer any
collisions.
 Only about 0.14% of the incident α-particles scatter by more than 1º
 Only about 1 in 8000 deflect by more than 90º.

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  Rutherford argued that, to deflect the α-particle backwards, it must experience a large
repulsive force.
 This force could be provided if the greater part of the mass of the atom and its positive
charge were concentrated tightly at its centre.
 Then the incoming α-particle could get very close to the positive charge without
penetrating it, and such a close encounter would result in a large deflection.
 This agreement supported the hypothesis of the nuclear atom.
 This is why Rutherford is credited with the discovery of the nucleus.
Rutherford’s nuclear model of the atom.
 The entire positive charge and most of the mass of the atom are concentrated in the
nucleus with the electrons some distance away. The electrons would be moving in
orbits about the nucleus just as the planets do around the sun.
 Rutherford’s experiments suggested the size of the nucleus to be about 10–15 m to
10–14 m.
Electrostatic force acting between alpha particle and the nucleus of Gold atom.
1 𝑞1 𝑞2
 Coulomb’s electrostatic force = 2
.
4𝜋𝜖0 𝑟
 Alpha particles are nuclei of helium atoms and, therefore, carry two units, 2e, of
positive charge and have the mass of the helium atom.
 The charge of the gold nucleus is Ze, where Z is the atomic number of the atom; for
gold Z = 79.
 Since the nucleus of gold is about 50 times heavier than an α-particle, it is reasonable
to assume that it remains stationary throughout the scattering process.
(𝑚 −𝑚 ) 2𝑚1 𝑢1
 ( Elastic collision from XI physics 𝑣1 = 1 2 𝑢1 , 𝑣2 = , when 𝑚2 >>𝑚1
𝑚1 +𝑚2 𝑚1 +𝑚2
ie. mass of gold nucleus is much greater than mass of alpha particle 𝑣2 = 0)

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Alpha-particle trajectory and impact parameter.
Under these assumptions, the trajectory of an alpha-particle can be computed employing
Newton’s second law of motion and the Coulomb’s law for electrostatic force of repulsion
between the alpha-particle and the positively charged nucleus.

 The trajectory traced by an α-particle depends on the impact parameter, b of collision.

 The impact parameter is the perpendicular distance of the initial velocity
vector of the α-particle from the centre of the nucleus.
 A given beam of α-particles has a distribution of impact parameters b, so that the
beam is scattered in various directions with different probabilities.
 It is seen that an α-particle close to the nucleus (small impact parameter) suffers large
scattering.
 In case of head-on collision, the impact parameter is minimum and the α-particle
rebounds back (θ ≅ π). ( v1 = -u1 elastic head-on collision m2 >> m1)
 For a large impact parameter, the α-particle goes nearly un-deviated and has a small
deflection.
 The fact that only a small fraction of the number of incident particles rebound back
indicates that the number of α-particles undergoing head on collision is small.
This, in turn, implies that the mass of the atom is concentrated in a small volume.
Rutherford scattering therefore, is a powerful way to determine an upper limit to the
size of the nucleus.
Distance of Closest Approach.
 The key idea here is that throughout the scattering process, the total mechanical
energy of the system consisting of an α-particle and a gold nucleus is conserved.
 The system’s initial mechanical energy is Ei, before the particle and nucleus interact,
and it is equal to its mechanical energy Ef when the α-particle momentarily stops.
 The initial energy Ei is just the kinetic energy K of the incoming α- particle.
 The final energy Ef is just the electric potential energy U of the system.
 The potential energy U can be calculated from V= W/q

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 1 𝑄
 V= , Q is the source charge ie. charge of the nucleus.
4𝜋𝜖0 𝑟
 Q = Ze, where Z is the atomic number of the atom ‘e’ is the charge of a proton.
 W = Vq (q is the charge of the alpha particle ie. 2e)
 Let d be the centre-to-centre distance between the α-particle and the gold nucleus
when the α-particle is at its stopping point and reverses its direction ie. Distance of
Closest Approach. (Angle of scattering is 180o)
 V is the electro static potential due to the nucleus of the Gold atom at a distance ‘d’.
1 𝑍𝑒
 V=
4𝜋𝜖0 𝑑
1 𝑍𝑒2𝑒
 W= (Work done to stop the alpha particle)
4𝜋𝜖0 𝑑
 (Work done to stop the alpha particle is converted in to potential energy -Work
energy theorem)
1 2𝑍𝑒 2
 ie. U =
4𝜋𝜖0 𝑑
 At the distance of closest approach the alpha particle stops so it’s entire K is
converted in to U
 U = K ( Mechanical energy is conserved in elastic collision)
1 2𝑍𝑒 2
 K=
4𝜋𝜖0 𝑑
1 2𝑍𝑒 2
 d= metre
4𝜋𝜖0 𝐾

Electron orbits.
 Atom is an electrically neutral sphere consisting of a very small, massive and
positively charged nucleus at the centre surrounded by the revolving electrons in their
respective dynamically stable orbits.
 The electrostatic force of attraction, Fe between the revolving electrons and the
nucleus provides the requisite centripetal force (Fc) to keep them in their orbits. Thus,
for a dynamically stable orbit in a hydrogen atom
𝐹𝑒 = 𝐹𝑐 ----------------------- (1)

𝑚v2 1 𝑒2
= ----------------------- (2)
𝑟 4𝜋𝜖0 𝑟 2

1 𝑄𝑞
[ Fe = , Q charge of the nucleus, q charge of an electron]
4𝜋𝜖0 𝑟 2

2 1 𝑒2
𝑚v = ----------------------- (3)
4𝜋𝜖0 𝑟
1 𝑒2
From (3) 𝑟 = ----------------------- (4)
4𝜋𝜖0 𝑚v2
‘r’ is the radius of the orbiting electron.
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We know
2 2 1 𝑒2
K= ½ 𝑚v From (3) 𝑚v =
4𝜋𝜖0 𝑟
 Kinetic energy of orbiting electron is
1 1 𝑒2
∴𝐾= ×
2 4𝜋𝜖0 𝑟

1 𝑒2
𝑖𝑒. 𝐾 = ----------------------- (5)
8𝜋𝜖0 𝑟
−1 𝑄𝑞
Electrostatic potential energy is 𝑈 =
4𝜋𝜖0 𝑟
−1 𝑒2
 Kinetic energy of orbiting electron is 𝑈 = -------------- (6)
4𝜋𝜖0 𝑟
 Total energy of orbiting electron is E = K + U
1 𝑒2 1 𝑒2
𝑖𝑒. 𝐸 = −
8𝜋𝜖0 𝑟 4𝜋𝜖0 𝑟

1 𝑒2 1 1 1 𝑒2
𝐸= [ − 1] = − 2 × 4𝜋𝜖
4𝜋𝜖0 𝑟 2 0 𝑟

1 𝑒2
𝐸=−
8𝜋𝜖0 𝑟
𝐽𝑜𝑢𝑙𝑒 -------------- (7)
 The total energy of the electron is negative.
 This implies the fact that the electron is bound to the nucleus.
 If ‘E’ were positive, an electron will not follow a closed orbit around the nucleus. It
will leave the nucleus. ( Ionisation )

ATOMIC SPECTRA.

 When an atomic gas or vapour is excited at low pressure, usually by passing an

electric current through it, the emitted radiation has a spectrum which contains
certain specific wavelengths only.
 In such spectra each and every wave length is observed as a bright line in a dark
background and called as line spectra. Each line corresponds to a particular
wavelength.
 A spectrum of this kind is termed as emission line spectrum
 Study of emission line spectra of a material can therefore serve as a type of
“fingerprint” for identification of the gas.
 When white light passes through a gas and we analyse the transmitted light using a
spectrometer we find some dark lines in the spectrum. ( White light has a continuous
spectra ie. it has all possible wave lengths in the visible region)
 These dark lines correspond precisely to those wavelengths which were found in the
emission line spectrum of the gas.
 This is called the absorption spectrum of the material of the gas.
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 The spacing between lines within certain sets of the hydrogen spectrum decreases in
a regular way.
 Each of these sets is called a spectral series.
 First such series was observed by a Swedish school teacher Johann Jakob Balmer in
the visible region of the hydrogen spectrum.
 This series is called Balmer series.
 As the wavelength decreases, the lines appear closer together and are weaker in
intensity.
 Balmer found a simple empirical formula for the observed wavelengths

1 1 1
= 𝑅( 2− ), n = 3, 4, 5 . . .
𝜆 2 𝑛2

 Where λ is the wavelength,

 R is a constant called the Rydberg constant, and the value of R is 1.097 × 10 7 m–1.
 ‘n’ may have integral values 3, 4, 5, etc.
 This equation is also called Balmer formula.

 Other series of spectra for hydrogen were subsequently discovered.

 These are known, after their discoverers, as Lyman, Paschen, Brackett, and Pfund
series.
 These are represented by the formulae

1 1 1
 Lyman series = 𝑅( 2− ), n = 2, 3, 4, 5 . . .
𝜆 1 𝑛2

1 1 1
 Paschen series = 𝑅( 2− ), n = 4, 5, 6, 7 . . .
𝜆 3 𝑛2

1 1 1
 Brackett series = 𝑅( 2
− ), n = 5, 6, 7, 8 . . .
𝜆 4 𝑛2

1 1 1
 Pfund series = 𝑅( 2− ), n = 6, 7, 8, 9 . . .
𝜆 5 𝑛2

Page 6 of 13
  The Lyman series is in the ultraviolet region.
 The Balmer series is in the visible region.
 The Paschen and Brackett series are in the infrared region.

 The Balmer formula may be written in terms of frequency of the light.

 𝑐=𝑣λ
𝑐
 =𝑣
𝜆

1 𝑣 1 1
 = = 𝑅( − )
𝜆 𝑐 22 𝑛2

1 1
 𝑣 = 𝑐𝑅 ( 2 − )
2 𝑛2

BOHR MODEL OF THE HYDROGEN ATOM

Drawbacks of Rutherford’s model of the atom
 It is assumed that the atom, consisting of a central nucleus and revolving electron is
stable much like sun-planet system which the model imitates.
 However, there are some fundamental differences between the two situations.
 While the planetary system is held by gravitational force, the nucleus-electron system
being charged objects, interact by Coulomb’s Law of force.
 We know that an object which moves in a circle is being constantly accelerated – the
acceleration being centripetal in nature.
 According to classical electromagnetic theory, an accelerating charged particle emits
radiation in the form of electromagnetic waves.
 The energy of an accelerating electron should therefore, continuously decrease.
 When energy of electron continuously decrease velocity of electron continuously
decrease.
 When velocity of electron continuously decrease radius of the orbit continuously
decrease.
 So the electron would spiral inward and eventually fall into the nucleus.
 Thus, such an atom cannot be stable.
 Further, according to the classical electromagnetic theory, the frequency of the
electromagnetic waves emitted by the revolving electrons is equal to the frequency
of revolution.
 As the electrons spiral inwards, their angular velocity continuously changes and
hence their frequencies would change continuously, and so the frequency of the light
emitted will change continuously.
 Thus, they would emit a continuous spectrum, in contradiction to the line spectrum
actually observed.
 Clearly Rutherford model tells only a part of the story implying that the classical
ideas are not sufficient to explain the atomic structure
Page 7 of 13
  Bohr combined classical and early quantum concepts and gave his theory in the
form of three postulates.
 Bohr’s first postulate was that an electron in an atom could revolve in certain stable
orbits without the emission of radiant energy.
According to this postulate, each atom has certain definite stable states in which it
can exist, and each possible state has definite total energy.
These are called the stationary states of the atom.
 Bohr’s second postulate defines these stable orbits. This postulate states that the
electron revolves around the nucleus only in those orbits for which the angular
momentum is some integral multiple of h/2π where h is the Planck’s constant
(6.6 × 10–34 J s).
Thus the angular momentum (L) of the orbiting electron is quantised.
That is L = nh/2π.
 Bohr’s third postulate states that an electron might make a transition from one of its
specified non-radiating orbits to another of lower energy. When it does so, a photon
is emitted having energy equal to the energy difference between the initial and final
states. The energy of the emitted photon is then given by hν = Ei – Ef
Quantisation of the radius, velocity and energy of an orbiting electron.
 From Bohr’s second postulate of quantisation angular momentum ,the angular
ℎ
momentum of the orbiting electron in the nth is given as 𝐿𝑛 = 𝑛
2𝜋
 From mechanics 𝐿𝑛 = 𝑚𝑟𝑛 v𝑛
ℎ
 Equating the equations 𝐿𝑛 = 𝑛 = 𝑚𝑟𝑛 v𝑛
2𝜋
ℎ
ie. 𝑟𝑛 = 𝑛 ----------------------------(1)
2𝜋𝑚v𝑛
1 𝑒2
From Rutherford’s model of the atom 𝑟 =
4𝜋𝜖0 𝑚v2
1 𝑒2
For nth orbit 𝑟𝑛 = ----------------------------(2)
4𝜋𝜖0 𝑚v2𝑛
Equating equations (1) & (2)

ℎ 1 𝑒2
𝑛 =
2𝜋𝑚v𝑛 4𝜋𝜖0 𝑚v2𝑛

1 𝑒2
𝑛ℎ =
2𝜖0 v𝑛

1 𝑒2
v𝑛 =
2𝜖0 𝑛ℎ

1 𝑒2
v𝑛 = × ----------------------------(3)
𝑛 2𝜖0 ℎ
Velocity of the orbiting electron in the nth orbit.
Page 8 of 13
Substituting vn from eqn.(3) in eqn. (1)
ℎ 𝑛ℎ2𝑛ℎ𝜖𝑜 𝜖𝑜
𝑟𝑛 = 𝑛 𝑒2
= = 𝑛2 ℎ 2
2𝜋𝑚[ 2𝑛𝜖 ℎ] 2𝜋𝑚𝑒2 𝜋𝑚𝑒2
𝑜
ℎ2 𝜖𝑜
𝑟𝑛 = 𝑛2 ----------------------------(4)
𝜋𝑚𝑒2
Radius of the nth orbit
ℎ2 𝜖𝑜
When n =1, 𝑟1 =
𝜋𝑚𝑒2
Which is also called as Bohr radius, represented by the symbol a0
ℎ2 𝜖𝑜
𝑎0 = , substituting the constants 𝑎0 = 5.29 × 10−11 𝑚 -------(5)
𝜋𝑚𝑒2

To find the energy of the orbiting electron in the nth orbit substitute rn in the expression for
1 𝑒2
of energy of the orbiting electron in Rutherford’s model of the atom 𝐸 = −
8𝜋𝜖0 𝑟

1 𝑒2 𝑛2 ℎ2 𝜖𝑜
𝐸𝑛 = − 𝑟𝑛 =
8𝜋𝜖0 𝑟𝑛 𝜋𝑚𝑒2
1 𝑒2 1 𝑒2 𝜋𝑚𝑒2
𝐸𝑛 = −
8𝜋𝜖0 𝑛2 ℎ2 𝜖
= − 8𝜋𝜖 2
𝑜 0 𝑛2 ℎ 𝜖𝑜
𝜋𝑚𝑒2

1 𝑚𝑒4
𝐸𝑛 = − ----------------------------(6)
𝑛2 8ℎ2 𝜀2
𝑜
substituting the constants
1 −18
𝐸𝑛 = − 2 × 2.18 × 10 𝐽
𝑛
Atomic energies are often expressed in electron volts (eV) rather than joules.
Since 1 eV = 1.6 × 10–19 J,
13.6
𝐸𝑛 = − 2 𝑒𝑉
𝑛
The negative sign of the total energy of an electron moving in an orbit means that the
electron is bound with the nucleus.
Energy levels
 The energy of an atom is the least (largest negative value) when its electron is
revolving in an orbit closest to the nucleus i.e., the one for which n = 1.
 For n = 2, 3, ... energy is progressively larger in the outer orbits.
 The lowest state of the atom, called the ground state, is that of the lowest energy,
with the electron revolving in the orbit of smallest radius, the Bohr radius, a0.
 The energy of this state (n = 1), E1 is –13.6 eV.

Page 9 of 13
  Therefore, the minimum energy required to free the electron from the ground state
of the hydrogen atom is 13.6 eV.
 It is called the ionisation energy of the hydrogen atom.
 This prediction of the Bohr’s model is in excellent agreement with the experimental
value of ionisation energy
 At room temperature, most of the
hydrogen atoms are in ground state.
 When a hydrogen atom receives energy
by processes such as electron collisions,
the atom may acquire sufficient energy to
raise the electron to higher energy states.
 That is the atom is in an excited state.
When n = 2
13.6 13.6
E2 =− 2 𝑒𝑉 = − 4
= −3.40𝑒𝑉
2
It means that the energy required to excite
an electron in hydrogen atom to its first
excited state, is an energy equal to
E2 – E1 = –3.40 eV – (–13.6) eV
= 10.2 eV.
 Similarly
13.6 13.6
 𝐸3 − 2 𝑒𝑉 = − = −1.51𝑒𝑉
3 9

 E3 – E1 = 12.09 eV, or to excite the hydrogen atom from its ground state (n = 1) to second
excited state (n = 3), 12.09 eV energy is required, and so on.
 From these excited states the electron can then fall back to a state of lower energy,
emitting a photon in the process.
 The principal quantum number n labels the stationary states in the ascending order of
energy.
 In this diagram, the highest energy state corresponds to n =∞ and has an energy of 0 eV.
 This is the energy of the atom when the electron is completely removed (r = ∞) from the
nucleus and is at rest.
 Energies of the excited states come closer and closer together as n increases.
 An electron can have any total energy above E = 0 eV. In such situations the electron is
free. Thus there is a continuum of energy states above E = 0 eV.
THE LINE SPECTRA OF THE HYDROGEN ATOM
Explanation based on Bohr model of the hydrogen atom
 According to the third postulate of Bohr’s model, when an atom makes a transition
from the higher energy state with quantum number ni to the lower energy state with
quantum number nf (nf < ni), the difference of energy is carried away by a photon of
frequency ν such that
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  hν = Ei – Ef 1 𝑚𝑒4 1 𝑚𝑒4
 hν = − 2 2 2 − [− 2 2 2 ]
𝑛𝑖 8ℎ 𝜀𝑜 𝑛𝑓 8ℎ 𝜀𝑜
1 𝑚𝑒4
 𝐸𝑖 = − 𝑚𝑒4 1 1
𝑛2𝑖 8ℎ2 𝜀2
𝑜  hν = [ 2 − 2]
2
8ℎ 𝜀2
𝑜 𝑛𝑓 𝑛 𝑖
1 𝑚𝑒4 𝑚𝑒4
 𝐸𝑓 = − 2 2 2  ν= [ 2
1
− 2]
1
𝑛𝑓 8ℎ 𝜀𝑜 3
8ℎ 𝜀2
𝑜 𝑛𝑓 𝑛 𝑖


 Dividing both sides by ‘c’ the speed of light,

ν 𝑚𝑒4 1 1
 = 3 2 [ − 𝑛2 ]
𝑐 8ℎ 𝜀2
𝑜 𝑐 𝑛𝑓 𝑖

ν 1 𝑚𝑒4 1 1
 = = [ − 𝑛2 ]
8ℎ3 𝜀2
2
𝑐 λ 𝑜 𝑐 𝑛𝑓 𝑖
𝑚 𝑒4
 = 1.03 × 107 𝑚−1 ≃ 1.097 × 107 𝑚−1 𝑅, 𝑅𝑦𝑑𝑏𝑒𝑟𝑔 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
8ℎ3 𝜀2
𝑜𝑐
1 1 1
 = R[ − 2] 𝐵𝑎𝑙𝑚𝑒𝑟 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛
λ 𝑛2𝑓 𝑛 𝑖

Explanation for different spectral series.

 Lyman series
electron make transitions to
nf = 1 from ni = 2,3,4 …
1 1 1
ie. = 𝑅 ( 2 − 2 ) 𝑛 = 2,3,4 …
𝜆 1 𝑛
 Balmar series
electron make transitions to
nf = 2 from ni = 3,4,5 …
1 1 1
ie. = 𝑅 ( 2 − 2 ) 𝑛 = 3,4,5 …
𝜆 2 𝑛
 Paschen series
electron make transitions to
nf = 3 from ni= 4,5,6 …
1 1 1
ie. = 𝑅 ( 2 − 2 ) 𝑛 = 4,5,6 …
𝜆 3 𝑛
 Brackett series
electron make transitions to
nf = 4 from ni = 5,6,7 …
1 1 1
ie. = 𝑅 ( 2 − 2 ) 𝑛 = 5,6,7 …
𝜆 4 𝑛
 Pfund series
electron make transitions to
nf = 5 from ni = 6,7,8 …
1 1 1
ie. = 𝑅 ( 2 − 2 ) 𝑛 = 6,7,8 …
𝜆 5 𝑛

Page 11 of 13
DE BROGLIE’S EXPLANATION OF BOHR’S SECOND POSTULATE OF QUANTISATION.

Basic requirement to understand this topic is standing waves in a string.

 When a string is plucked, a vast number of wavelengths are excited.
 However only those wavelengths survive which have nodes at the ends and form
the standing wave in the string.
 It means that in a string, standing waves are formed when the total distance
travelled by a wave down the string and back is one wavelength, two
wavelengths, or any integral number of wavelengths.
 Waves with other wavelengths interfere with themselves upon reflection and
their amplitudes quickly drop to zero.
 According to Louis de Broglie the electron in its circular orbit must be seen as
a particle wave.
 In analogy to waves travelling on a string, particle waves too can lead to
standing waves under resonant conditions.
 For an electron moving in nth circular orbit of radius rn, the total distance is the
circumference of the orbit, 2πrn.
 According to de Broglie 2πrn = n λ , n = 1, 2, 3 . . .
 Figure illustrates a standing particle
wave on a circular orbit for n = 4,
i.e., 2πrn = 4 λ , where λ is the de
Broglie wavelength of the electron
moving in nth orbit.
 λ = h/p, where p is the magnitude of
the electron’s momentum.
 If the speed of the electron is much
less than the speed of light, the
momentum is mvn.
Thus, λ = h/mvn.
2π rn = n h/mvn or
mvn rn = nh/2π
ie. Angular momentum of the
electron in the nth orbit is nh/2π.

Limitations of Bohr’s model of Atom.

 The Bohr model is applicable to hydrogenic atoms.
It cannot be extended even to mere two electron atoms such as helium.
Difficulty lies in the fact that each electron interacts not only with the positively
charged nucleus but also with all other electrons.
The formulation of Bohr model involves electrical force between positively
charged nucleus and electron. It does not include the electrical forces between
electrons which necessarily appear in multi-electron atoms.

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 While the Bohr’s model correctly predicts the frequencies of the light emitted
by hydrogenic atoms, the model is unable to explain the relative intensities of
the frequencies in the spectrum.
In emission spectrum of hydrogen, some of the visible frequencies have weak
intensity, others strong. Experimental observations depict that some transitions
are more favoured than others.
Bohr’s model is unable to account for the intensity variations

A useful formula to calculate Energy of a photon in eV

Energy in eV = 12400 / wave length of the radiation in Ao
It saves lot of time in solving the numerical like this one

(1) 𝜆1 = 390𝑛𝑚 = 390 × 10−9 𝑚 = 3900 × 10−10 𝑚 = 3900𝐴𝑜

12400
𝐸1 = = 3.179 𝑒𝑉
3900

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