Introduction to Atomic structure

Line Spectra
 We can use a prism or a diffraction grating to separate the various wavelengths in a
beam of light into a spectrum.(plural spectra)
 If the light source is a hot solid such as a light bulb or liquid, the spectrum is
continous; light of all wavelengths is present. Fig 38.1a
 But if the source is a gas carrying an electric discharge as in neon sign or a volatile
salt heated in a flame, only a few colours appear, in the form of isolated sharp parallel
lines fig 38,1b.
 A spectrum of this sort is called line spectrum. Each line corresponds to a definite
wavelenght and frequency.
 It was discovered early in the 19th century that each element in its gaseous state has a
unique set of wavelenghts in its spectrum.
 A spectrum of hydrogen always contains a certain set of wavelengths; Sodium
produces a different set, iron still another.
 Scientists use spectra to identify elements and compounds. As per the photo on top of
the page.
 The characteristic spectrum of an atom was presumably related to its internal
structure, but attempts to understand this relationship solely on the basis of classical
mechanics and electrodynamics were not successful.
 

X-Rays

 Other unsolved problems in the emission and absorption of radiation centred on the
production and scattering of x rays discovered in 1895.
 These rays were produced in high voltage electric discharge tubes, but no one
understood how and why they were produced or what determined their wavelengths,
which are much shorter than those of visible light.
 Even worse, when x rays collided with matter, the scattered rays sometimes had
longer wavelengths than the original ray. This is analogous to a beam of blue light
striking a mirror and reflecting back as red.

To investigate all this factors let us visit the structure of the atom

a) The Thomson model 1898

b) The Rutherford atomic model
Rutherford speculated that electrons must circle the nucleus in some way. This introduced
instability problem

Rutherford Atomic model which was unsatisfactory and unstable because according to
classical mechanics and electromagnetic theory, any charged particle moving on a curved
path emits em radiations. Thus, electrons would lose energy and spiral into the nucleus in a
short time (Fig 1). Hence atoms would not exist
 Figure 1

c) Neil Borh atomic model

To remedy the stability problem, Bohr postulated that

1. electrons move in orbits of fixed size and energy.

 2. The energy of an electron depends on the size of the orbit and is lower for small
orbits.
3. Radiation can only occur only when the electron jumps from one orbit to another
4. The atom would be completely stable in the state with smallest orbit, since there is no
orbit of lower energy into which the electron can jump.

Using Plank’s constant Bohr obtained an accurate formula for the energy levels of the
hydrogen atom

1. He postulated that the angular momentum of the electron is quantized i.e it can only
have discrete values
2. Because of quantization, the electron orbits have fixed sizes and energies.
3. The orbits are labelled by an integer, quantum number n.
4. Energy is emitted from the atom when the electron jumps from one orbit to another
closer to the nucleus.

Shown here is the first Balmer transition, in which an electron jumps from orbit n=3 to orbit
n=2, producing a photon of red light with energy of 1.89 eV and a wavelength of 656 x 10-9 m
(656 nm).

If an electron jumps one orbit closer to the nucleus, it must emit energy equal to the
difference of the energies of the two orbits. Conversely, when the electron jumps to a larger
orbit, it must absorb a quantum of light equal in energy to the difference in orbits
−34
E=Ef −Ei h=6.627 x 10 js E f −final energy E i−initial energy

With these conditions Bohr was able to explain emission spectrum of hydrogen
Four more series of lines were discovered in the emission spectrum of hydrogen, by
searching the infrared spectrum at lower wavelengths and the ultraviolet spectrum at shorter
wavelengths. Each of these lines fits the same general equation, where n1 ,∧n1 are integers
and R H is 1.096 x 10 -2 nm-1

1
λ [1 1
=R H 2 − 2
n 1 n2 ]
In addition, any moving object in a straight line has momentum

P=mv 1

An object moving in a circular orbit has an angular momentum

L=rxp 2

Substituting equation 1 into 2 we get

L=mvr

Bohr assumed that the angular momentum of the electron can take only certain values, equal
to an integer times Planks constant divided by 2 π

mvr=n ( 2hπ ) where n=1, 2 , 3 … … .

Bohr then used classical physics to show that energy of an electron in any one of these orbits
is inversely proportional to the square of integer n. The difference in energies of any two
orbits is

∆ E=R H
[ 1 1
2
]
− 2 where R H is called Rydberg constant R H is 1.096 x 10 -2 nm-1
n1 n2

Planks equation states energy of a photon

c
E=hf but since c=fλwe have E=h
λ

Example

Calculate the wavelength of light given off by a hydrogen atom when an electron falls from
n=4 to the n =2 orbit in Bohr model

Solution

When electron falls from n =4 to n =2 wavelength becomes

1
λ
=1.096 x 10
−2 1
2
[1
− 2
21 4 2 ] hence λ=486.3 nm
Total energy of an atom
(Borhs quatum model of the atom)
Need to recall concepts learnt in SPH 101 Electricity and magnetism like
 Electric potential energy U = Force (F) x distance (d) 1
1
 Force between two charged particles F= q q
2 1 2 2
4 π εo r
1
Substitute equation 2 into 1 to get U = q q xr
2 1 2
4 π εo r
1
U= q q is the electric potential energy
4 π εo r 1 2
k 2
which can also be written as U= e
r

Where we have assumed that the force F acts through a distance (d) = r

1 2
We can also find an expression for kinetic energy K . E= me v
2
In the figure below we notice that coulomb force must equal centripetal force

2
1 2 me v
2
e=
4 π ε or r

k 2 me v 2
2
e =
r r

2
2 e
me v =k
r

2 2
mv e
KE= = k
2 2r
 2
e
KE=k Kinetic energy
2r

Total energy of the atom

The total energy of the atom E = KE + U

2
e k 2
E =k - e
2r r
Minus sign, arise due to negative charge of the electron

2 2 2
k e −2 k e e
E= =−k
2r 2r

Total energy of the atom 9

Note that the total energy is negative, indicating a bound electron proton system.
2
e
This means that energy in the amount of −k must be added to the atom to
2r
remove the electron and make the total energy of the system zero.

Quantizantion of radius and energy

 We can obtain an expression for r the radius of the allowed orbits, by solving
equations 6 and equation 6.26

2 2
mv e
= k 6
2 2r
2
2 ke
v= 11
r me

Equation 10, me vr=nћ gives

( )
2
2 nћ
v= 12
me r

Equating equation 11 and 12

( )
2 2
2 ke nћ
v= ¿
r me me r

ћ 2
rn = 2
n 13
me k e

n=1 ,2 , 3 , … … …
This equation shows that the radii have discrete values- they are quantized. The result
is based on the assumption that the electron can exist only in certain allowed orbits
determined by the integer n.
The orbit with the smallest radius, called Borh radius a o, corresponds to n=1 and has
2
ћ
the value a o= 2 = 0.0529 nm 14
me k e

Circumference of the electron orbit c = 2 πr = 2 πx 5.29 x 10−11 = 33.238x10−11 m

Quantization of energy

We obtain a general expression for the radius of any orbit in hydrogen atom by
substituting equation14 into 13
2 2
r n =n ao=n ( 0.00529nm )
The quantization of orbit radii immediately leads to energy quantization. We
substitute r n =n2 ao into equation 9

( )
2
−k e 1
En = n=1,2,3…………………………..
2 ao n2

Inserting numerical values

 13.606 eV
En = 2 n=1,2,3…………………………….
n

Only energies satisfying this equation (called energy levels) are permitted. The lowest
energy level, called ground state has n=1 and energy E1=−13.606 eV . the next energy level,
E1
the first excited state , has n=2 and energy E2= 2 =−3.401 eV
2

The energy level diagram

n- are called quantum number

the outermost level n = ∞ with E=0 represent the state for which the electron is removed from
the atom.

The minimum energy required to ionize an atom (that is to completely remove an electron in
ground state from the proton’s influence is called ionisation energy. As can be seen from the
figure, the ionisation energy for hydrogen in the ground state is 13.6 ev

Assignment
Define
 Quasar
 Blackhole
 Gravitational red shift