ATOMIC STRUCTURE

FUNDAMENTAL PARTICLES

Atom is the smallest unit of an element which retains the characteristic properties of the element. An
atom can be seen in a powerful microscope called scanning tunnelling microscope (STM).
Electron:
Charge(q) = – 1.602 × 10-19 coul(one unit of negative charge i.e –1)
Mass(m) = 9.1×10-28gm = 9.1×10-31 kg = 0.0005486 amu
Proton:
It is 1836 times heavier than an electron.
Charge(q) = + 1.602 × 10-19 coul(one unit of positive charge i.e +1)
Mass(m)= 1.66 ×10-24gm = 1.67 ×10-27kg = 1.00727 amu
Neutron:
Neutron is slightly heavier than proton(compare their masses in amu).
Charge(q) = 0; Mass(m)= 1.67×10-24gm = 1.67×10-27kg = 1.00866 amu

RUTHERFORD'S MODEL OF ATOM

Rutherford gave his model of atom after conducting his famous gold foil experiment by which nucleus of atom
was discovered.
Atom consists of two parts: (i)Nucleus (ii)Extra-nuclear part
Nucleus:
Nucleus is the extremely minute spherical body situated at the centre of the atom. Nucleus carries negligible
volume compared to the total volume of the atom. But it contains 99.95-99.98% of its total mass. It carries
all protons and all neutrons. This means that it carries all the positive charge and almost all the mass of the
atom because electrons carry negligible mass. Its radius was calculated by Rutherford to be 2.72 × 10-12cm.
In other words, almost the whole mass of the atom is concentrated in a very tiny point called nucleus.
Extra-nuclear Part:
The part of the atom other than nucleus is called the extra-nuclear part. Most of the space occupied by
this part is empty or vacant. Electrons are situated far away from the nucleus and revolve continuously round
the nucleus just like planets revolve round the sun in the solar system. Therefore electrons were designated
as planetary electrons. The radius of an atom i.e the size of the extra-nuclear part (note that the extranuclear
part embeds the nucleus inside it) is approximately 10-8 cm. Thus nucleus is nearly 10,000 times smaller in
size than the atom.
So nucleus of an atom is responsible for the mass of the atom while the extra-nuclear part is responsible
for the volume of the atom.

Rutherford's Gold Foil Experiment: (DISCOVERY OF NUCLUES)

A radioactive metal polonium was taken in a lead box with a narrow hole. Polonium is an emitter of alpha
particles. Alpha particles are nothing but the dipositive helium ions(He++) which are spontaneously emitted
from radioactive elements such as polonium. A thin beam of very high speed alpha particles were allowed
to come out from the lead box through the fine hole and that is then allowed to strike on a very thin gold
foil of 0.00004cm thickness. A movable fluorescent screen (ZnS) was placed behind the gold foil to monitor
the path of the alpha rays after the beam strikes on the gold foil. Note that when alpha particles strike on
a fluorescent screen, the screen produces bright light at the spot where the particles strike. The following
observations were made.

(i) Most of the alpha particles penetrated straight through the gold foil without any deviation in its
direction of motion. The thin beam of the particles almost fell straight onto the ZnS screen where it produced
a bright glow. This was not a new observation made by Rutherford as it was known before that radioactive
rays can penetrate through thin metallic foils and sheets.
(ii) His remarkable observation was that a few alpha particles were deviated from their original directions
of motion and deflected at different angles. This was known by using a circular ZnS screen to different
positions and verifying whether any glow appears or not. Faint glow appeared at different angles in the ZnS
screen which confirmed the above observation.
(iii) The most remarkable observation was that a very few alpha particles (about 1 in about 20,000)
rebounded back after hitting the gold foil.

Explanation:
(i) Since most of the alpha particles passed through the gold foil straight without suffering any deviation
in their path, most of the space occupied by the atom must be empty.
(ii) Since a few alpha particles were deviated at different angles, there must be a minute but very heavy
body at the centre of the atom which carries all the positive charges and almost all the mass of the atom.
Those few alpha particles which pass near this heavy +vely charged body, suffer repulsion and deviate at
different angles with respect to their original direction. You already know that alpha particles are dipositive
helium ions for which they suffer repulsion when they pass near the heavy +vely charged body(nucleus of
gold atom) located at the centre of the atom. This heavy positively charged body was named as nucleus.
(iii) Those very few alpha particles which directly hit on the heavy positively charged minute body(nucleus)
rebounded back without passing through the gold foil. Thus the presence of the nucleus is further confirmed
by this observation.
Radius of nuclues: The approximate radius of nucleus was determined from the following formula.
1
-13 3
rn = 1.4 X 10 A cm (where A= mass number of the element)
SAQ 1:
(i) Why is polonium taken in a lead box?
(ii) Why can the alpha particles not dislodge and remove the nucleus from the atom by hitting onto it
rather themselves get rebounded?
(iii) Why gold was chosen for the experiment?
(iv) How the fundamental particle neutron was discovered?

Electromagnetic Radiations:
Electromagnetic radiations are forms of energy of different magnitudes which travel in the form of transverse
waves. These waves are simply energy waves and do not carry any mass like the matter waves. A wave
has three parameters to describe it. These are called wavelength (λ), frequency (ν) and wave-number(  ).
Only one of the parameters is required to identify a particular wave and distinguish it from others. The other
two parameters are automatically known.
Crest and Trough: The top(maximum) position of a wave is called crest and the bottom(minimum)
position is called trough.
(i) Wave length(λ λ ): It is the distance between two adjacent crests or two adjacent troughs of a
wave. It is expressed in distance units i.e cm(CGS) and m(MKS). But usually the wavelengths of electromagnetic
waves are so small that they are expressed in angstrom represented by (Å) or nanometer(nm) units.
1 Å = 10-8cm = 10-10m 1nm= 10-9m = 10-7cm
SAQ 2: The wavelength of a wave is 0.001cm. Express in Å as well as nm units.
SAQ 3: The wavelength of a wave is 1000Å. Express it in cm and m units.
(ii) Frequency(ν ν ): The number of full waves passing through a particular point per second is
called frequency. The unit of frequency is waves/sec or cycles/sec (Hertz) or more commonly 1/sec or
sec -1 .

 = 1
(iii) Wave-number(  ): It is the reciprocal of wavelength.

Unit of wave number = 1/cm or cm-1 and 1/m or m-1.
(Note that the unit cannot be 1/Å or Å-1. So if the wavelength is given in Å unit, it is first converted to cm
or m unit and then its reciprocal is found out to get wavenumber).
Example: Calculate the wave-number of a wave which has a wavelength of 3000Å.
Solution: Wavelength= λ= 3000Å = 3000 X 10-8cm (Since 1Å = 10-8cm)
  
Wave-number =     .    cm 
    cm      
Example : Calculate the wavelength in angstrom unit if its wave-number 4000cm-1.

Solution: Since  =
1

8 4 0
0 4
A = 10,000
1 1 10 X 10
 = 4000 cm-1
= 4000
cm = 4000 4000
= 2.5 X 10 A ( 1 Å = 10-8cm ⇒ 1cm=108 Å.)

(Caution: Dont confuse with symbols  with ν. They are different parameters)
Electromagnetic Spectrum:
Different electromagnetic radiations are arranged in the order of increasing wavelengths. This
systematic arrangement of all the forms of electromagnetic radiations are called electromagnetic spectrum.
In fact, the radiations that are present in each type in the spectrum contains infinite number of waves having
wavelengths lying within a particular range.

Name of Radiation Wavelength Range in Å

Cosmic Rays 0.001 - 0.01

Gamma Rays(γ) 0.01 - 0.1
x-rays 0.1 - 150
ultraviolet(UV) Rays 150 - 3800
Visible Rays 3800 - 7600
Infrared(IR) Rays 7600- 6 × 106
Microwave 6 × 106 - 6 × 109
Radiowaves 6 × 109 - 3 × 1013

SAQ 4: Indicate to which type of electromagnetic radiations the following waves belong. The
wavelengths of the radiations are given below.
(i)3000Å (ii) 10Å (iii)104 Å (iv)0.05Å (v)120Å
8
(vi)10 Å (vii)0.005Å (viiii)6 × 103Å (ix)1011Å (x) 400 nm

RELATIONSHIP BETWEEN WAVELENGTH AND FREQUENCY:

Wavelength is inversely proportional to frequency. Mathematically,
1 1
ν ∝ ⇒  =k (where k is the proportionality constant)
 
k= νλ ⇒ (1/sec) × cm = cm/sec
So the unit of k becomes the unit of velocity. This k is designated as c for electromagnetic waves, which
is conventionally called the velocity of light. As a matter of fact this is the velocity of all electromagnetic
radiations such as ultraviolet, infrared, x-rays etc.
1
 =c ⇒  = c ⇒  =c

8 10
c= 3 × 10 cm/sec = 3 × 10 cm/sec

Example: The wavelength of an ultraviolet radiation is 2000Å. Calculate its frequency and wave-
number.
1
Solution: λ = 2000Å= 2000 × 10-8cm. We know that  = c

7
10
1 3000 X 10 15
So  = 3 X 10cm/secX -1
2000 X 10 = -8 = 1.5 X 10 sec
-8
2000 X 10
So the frequency of the wave is 1.5 X 1015 sec-1 or Hertz.
4
1 1 10
Again  = ⇒ = = =
4 -1
2000 X 10-8 cm 2000 X 10-8 X 10 cm 5 X 10 cm
4

So the wave-number of the radiation is 5 × 104 cm-1.
Example: The frequency of a certain electromagnetic wave is 1017 sec-1. Find its wavelength in angstrom
unit. Also find its wave number. Indicate to which region of the electromagnetic spectrum does it
belong.
Solution: ν = 1017 sec-1. So λ = c/ν = (3 × 1010)/1017
= 3 × 10-7 cm = 3 × 10-7 × 108 Å = 30 Å.
This wave belongs to x-rays of the electromagnetic spectrum(Refer table).
1
Wave-number =  = = 1/(3 × 10-7cm) = 3.33 × 106 cm-1.

Example: The wave-number of a certain electromagnetic spectrum is 4000 cm-1. Find its wavelength
in angstrom unit. Also find its frequency. To which region of the electromagnetic spectrum does this
wave belong.
Solution: λ = 1/  = 1/4000 cm = (1/4000) × 108 Å = 2.5 × 104 Å
This wave falls in the infrared(IR) region of the electromagnetic spectrum.
ν = c ×  = 3 × 1010 × 4000 = 1.2 × 1014 sec-1.
SAQ 5:
(i) What is the velocity of x-rays? How it is related with the velocity of infrared rays.
(ii) A certain electromagnetic radiation has a wavelength of 500 nm. What is its frequency
and wavenumber? To which region does it belong?
(iii) Arrange the following radiations in the order of increasing wavelengths.
microwave, x-rays, uv rays, cosmic rays and radiowaves.
(iv) Arrange all the electromagnetic radiations in the decreasing order of frequencies.
(v) Wavelength is inversely proportional to frequency. Indicate in which way the wavenumber
varies with frequency? Arrange the following in the increasing order of wave number.
visible rays, ultraviolet rays, gamma rays, microwaves.
(vi) Give one application of x-rays, gamma rays, microwave and radiowaves.
(vii) How many different waves are present in sunlight?
(viii) Where can we get ultraviolet radiations? What is its harmful effect?

PLANCK'S QUANTUM THEORY

Qualitative Aspect:
Planck suggested that the electromagnetic radiations do not move continuously as we expect of a transverse
wave. They travel in the form of discontinuous energy packets. These energy packets are called quanta
(singular-quantum)or photons. Although the term photon was originally used to represent a packet of light
energy(quantum), Einstein used the term to denote all types of electromagnetic radiations. These packets or
quanta were believed to be hypothetical particles having no rest mass. Thus the dual theory or corpuscular
theory of light was put forth by Einstein which says that light and in fact all electromagnetic radiations can
be considered both as waves as well as particles (corpuscles). The particles in this case are not real particles
but are the massless photons or quanta. For some phenomena of light, its wave nature is taken into consideration
and for some other phenomena the particle nature is considered. These photons are emitted from its source
and propagated in space absorbed by a body so fast that the discontinuity between successive photons cannot
be detected. The photon theory of light was corroborated by (1) Black Body radation(Planck), (2) Photoelectric
effect(Einstein), (3)Compton scattering effect and (4)atomic spectra.

(Einstein wrote "In fact, it seems to me that the observations on "black-body radiation",
photoluminescence, the production of cathode rays by ultraviolet light and other phenomena involving
the emission or conversion of light can be better understood on the assumption that the energy of light
is distributed discontinuously in space. According to the assumption considered here, when a light ray
starting from a point is propagated, the energy is not continuously distributed over an ever increasing
volume, but it consists of a finite number of energy quanta, localised in space, which move without
being divided and which can be absorbed or emitted only as a whole".)

Quantitative Aspect:
Planck proposed that the energy of each packet of electromagnetic radiation is directly proportional
ν). Mathematically
to the frequency of that wave(ν

E ∝ ν ⇒ E = h ν
For 'n' number of photons the total energy is E = n h ν
(where h= the proportionality constant called Planck's constant whose value is
h = 6.627 X 10-27 erg.sec or 6.627 X 10-34 joule.sec)
E = h = hc = hc

Example: Calculate the energy of a light photon having frequency 1014 sec-1(Hertz).
Solution: According to Planck's quantum theory, E = hν =6.627 × 10-27erg.sec×1014sec-1
= 6.627 × 10-13 erg (CGS).
In MKS unit, E = hν = 6.627 × 10-34 joule.sec × 1014 sec-1= 6.627 ×10-20joule.
Example: Calculate the energy of an ultraviolet photon whose wavelength is 300nm.
Solution: λ = 300 nm = 300 × 10-7cm. We know that
-27 10
6.627 X 10 erg.sec X 3 X 10 cm/sec
E = hc , So E = = 6.627 × 10-12 erg
 -7
300 X 10 cm
Example: Calculate the energy of a photon having wave-number 107 cm-1.
Solution: We know that E = hc ,
So E = 6.627 × 10-27 erg.sec × 3 × 1010 cm/sec × 107 cm-1 = 19.88 X 10-10 erg
= 1.988 X 10-9 erg.
Experssing energy in Einstein unit:
1 Einstein is the energy of 1 mole of photons of a particular type. This unit is now redundant for chemical
science. But still is use sometimes.
SAQ: Calculate the energy of 6.023 X 1018 photons having frequency 1014 s–1 both in J and in Einstein units.
Solution: E  nh  6.023  1018  6.627  10 34  1014  0.3991J
E nh n
E m  N A h     10 5 Einstein
E m N A h N A
SAQ 6:
(i) Energy of a photon of electromagnetic radiation is inversely proportional to the wavelength. Is the
statement true? Indicate their relation.
(ii) Between x-ray photon and IR photon, which is more energetic and why?
(iii) In the electromagnetic spectrum, which radiation is most energetic and which least?
Indicate its cause.
(iv) How does energy of a photon vary with wave-number?
(v) "A radioactive element emits gamma rays continuously i.e the energy is emitted continuously without
any break". Is the statement true? If not correctly justify.
(vi) Why do we not observe the discontinuity of any electromagnetic radiations: say visible radiations.
(vii) Calculate the energy of light photon having wavelength of 7000Å.
(viii) What will be the energy of a photon having frequency of 1015 sec-1?
(ix) Calculate the energy of a microwave photon having wavenumber 1 cm-1.
(x) The energy of a photon is 1.98 × 10-18 erg. Calculate its wavelength, frequency and wavenumber.
To which region of the electromagnetic spectrum does it belong.
ATOMIC SPECTROSCOPY
When a mixture of radiations of different wavelengths is allowed to pass through a prism, the individual
radiation gets separated or spread from lower wavelength to higher wavelength starting from bottom to top.
When white beam of sunlight is passed through a prism we observe seven colours starting from violet at
the lowermost part followed by indigo, blue, green, yellow, orange in the intermediate part and red at the
uppermost part(VIBGYOR). Violet colour has the smallest wavelength and red colour has the greatest
wavelength and the wavelength regularly increases from violet to red. Spectrum is a pattern of different
colours (VIBGYOR) that we see on a screen or on photographic plate when white light is allowed to
pass through a prism.
Spectrum is not only restricted to visible spectrum or the solar spectrum. It is extended to all the electromagnetic
radiations such as UV spectrum, IR spectrum, Microwave spectrum and so on. When a beam of ultraviolet
rays will pass through a prism, similar phenomenon occurs like the visible spectrum, the mixture gets
separated and disperse into a band of radiations with increasing wavelength from 150 to 3800Å as we move
from bottom to top. The difference is that there is no colour in this case like that we found in visible
spectrum, so we cannot observe them in our eyes on a screen. The very large number(in fact infinite) of
UV radiations in the range of 150 to 3800Å that are present in the beam get split and disperse into a wide
band which can only be seen on a photographic plate. This is the UV spectrum. Same is the case with IR
spectrum and in fact with the spectra of all electromagnetic radiations. So spectrum is a regular pattern or
arrangement of radiations of increasing wavelength from lower part to higher part that is observed either on
a screen or photographic plate. Excepting the visible(light)spectrum, no other spectrum can be observed on
a screen. All the spectra(singular: spectrum) can be recorded on a photographic plate. This is because
photographic plate is affected by all types of electromagnetic radiations.
SAQ 7:
(i) What colour will you get if you mix all the seven colours, VIBGYOR?
(ii) Which colour produces photons of the greatest energy which of least energy?
(iii) Green colour in the VIBGYOR spectrum refers to a single wavelength. Is this statement
true? Give reason.
(iv) Why violet light appears at the lowermost part of the visible spectrum?
(v) UV radiations fall in the range of 3800 Å to 7600Å of the electromagnetic spectrum.Which other
region of the electromagnetic spectrum has wavelength greater than 3800Å(and just above it) and which
region has wavelength smaller than 150Å(just below it)?
TYPES OF SPECTRA:
(i) Discontinuous or Line Spectrum:
In discontinuous or line spectrum there are a few discrete lines with a detectable separation between them.
When NaCl crystal is kept inside a flame, a golden yellow colour which is characteristic of sodium is emitted.
When this radiation is allowed to pass through a prism and the spectrum is viewed in a screen, only two lines
are observed in the yellow region of the spectrum. These yellow lines are called D1 and D2 lines of sodium
at 5890 and 5896Å respectively. These are well separated lines and hence not continuous. This type of
spectrum is called a discontinuous spectrum or a line spectrum.

Similary KCl kept in the flame produced a few discrete lines in the violet region in the spectrum. These few
radiations are characteristic of potassium. Like Na and K, calcium will emit brick red colour and barium will
emit pea green colour. Each of the colour on analysis through a prism gives a few lines well separated from
each other in the spectrum. These are the examples of discontinuous spectra. Spectrum of each element is
unique and gives fixed number of lines which are not superimposable with the spectra of another element.
Therefore spectrum is called the fingerprint of the element.

(ii) Continuous or Band Spectrum:

In a continuous or band spectrum there is no gap or discontinuity in the spectrum from start to end. Solar
spectrum is one such spectrum. The spectrum gives a band of colours starting from violet and ending in red.
As a matter of fact when a large number of lines are placed very close to each other and overlap with each
other, we get a band or continuous spectrum. The light coming from an electric bulb when analysed also give
a continous patch of colours, though not VIBGYOR found from sunlight.
SAQ 8:
(i) What is the nature of spectrum of elements: continuous or discontinuous?
(ii) "In line spectrum, we get a continuous band or patch of colours." Is the statement true or false?
Give reason.
(iii) "The seven colours in the solar spectrum are well separated from each other having
distinct gaps between them". State whether the statement is true or false. Give reason.
(iv) Explain why sodium metal as well as NaCl solid containing Na+ give the same golden
yellow line spectra(D1 and D2) ?
TYPES OF SPECTRA ON THE BASIS OF EMISSION AND ABSORPTION
1. Emission Spectra
When the spectrum of an element or a substance is taken while it is emitting radiations it is called
emission spectrum. Solar spectrum(VIBGYOR), sodium spectrum(D1 and D2 lines), the blue lines for the Cs
spectrum, violet lines for the K spectrum are examples of emission spectra. Most of the spectra studied come
under this category. It can be generally called the hot spectrum.
2. Absorption Spectra
When the spectrum of the substance is taken when it is absorbing radiation from sunlight or any other
continous spectral region, it is called absorption spectrum. It can be generally called Cold Spectrum.

When a beam of light coming from an electric bulb is passed through a prism and the spectrum
produced on a screen is analysed it gives a continous patch of colours. But when the beam of light coming
from a hot gas (say Ne, He or H2 etc.) is passed through a prism, a small number of well separated discrete
lines are obserbed. Both the two are examples of emission spectra, while the difference is the first one is
continuous spectrum of the bulb light and the second one is discontinuous or line spectrum of the specific
gas. On the other hand if a beam of light coming from the same electric bulb(1st case) is first passed through
the same gas(2nd case) kept in cold conditions, and the light coming out of the gas on the other side is
analysed through the prism, we get the same continuous patch as in (1) but a few lines are missing in it shown
by dark lines. This array of missing lines(dark lines) gives the absorption spectrum of the gas as shown int
eh 3rd experiment. The missing lines occur at the same positions as are found as coloured lines in the
emission spectrum of the gas(2nd experiment).
When a beam of sunlight is first passed through NaCl solution and then through a prism then the
spectrum is observed on a white screen the spectrum is found to contain the entire VIBGYOR pattern expect
two lines in the yellow region i.e D1(5890 Å) and D2(5896 Å) which appear as dark lines or missing lines.
This is because Na+ ions present in the solution have absorbed the two radiations(D1 and D2) from the
sunlight and that is why they are missing in the spectrum. In the diagram above, the VIBGYOR pattern has
been shown in dark shade and the missing lines are shown in white shade. The arrangement of these missing
lines is called the absorption spectrum. In the above case the D1 and D2 lines(missing lines) constitutes the
absorption spectrum of sodium.

Emission and absorption spectra of a substance give the same information, one directly and the other
in the indirect manner.

HYDROGEN SPECTRUM
When hydrogen gas is taken in a glass tube and is subjected to high voltage and very low pressure, it glows
by emitting a reddish white light. When this light is analysed by passing it through a prism or diffraction
grating(superprism) and the spectrum observed in a photographic plate, we see only few lines. Hence
hydrogen spectrum is a line or discontinuous spectrum. The lines approach closer and closer towards the
lower wavelength region and after few lines merge into each other to form a thin band called continuum.
The series of lines observed in the visible region is called Balmer series. In this series the first line appears
in the orange(6563Å) region, the second in the blue(4861Å), third in the violet region(4341Å) and further
lines start merging onto one another in the same violet region. Analysis through high resolution diffaction
gratings has revealed the existence of 4 closely spaced converging lines in the violet regions giving a total
of 6 lines in the visible region. In fact the merging of lines forming a thin band appears in the near UV region.
Balmer proposed the following empirical equation to calculate the frequency(ν) of the lines in the series.
15 1 1
 = 3.29 X 10 sec
-1 2
-
2 x2
(where x = 3, 4, 5, 6.... for the 1st, 2nd, 3rd, 4th lines of the series respectively)
After the discovery of Balmer series in the visible region, on careful analysis of the hydrogen spectrum in
regions other than visible, other series of spectra were discovered by different scientists. These are Lyman
series, Paschen series, Brackett series, Pfund series and Humphreys. Each series shows the same
pattern i.e consists of few lines which approach closer and closer and finally merge onto one another towards
the lower wavelength region forming a thin band. Lyman series falls in the ultraviolet region while the
remaining series of lines fall in the infrared region of the electromagnetic spectrum.(For details, see later)
SAQ 9:
(i) Hydrogen spectrum is discontinuous: State true or false
(ii) Solar spectrum and hydrogen spectrum belong to the same category of line spectrum.
State true or false.
(iii) What is a spectrometer and what are its functions?

BOHR'S MODEL OF ATOM

Demerits of Rutherford's Model of atom:
1. Rutherford's model could not explain the discontinuous nature of hydrogen spectrum(Balmer series).
2. According to the theory of electrodynamics, if a charge particle like electron(-ve) revolves round
another charged particle(nucleus:+ve), the electron should continuously lose or emit energy and therefore
should gradually be drawn nearer to the nucleus and finally should merge onto the nucleus. If that would have
really happened, then there would not have existed any proton or electron separately as they would have
destroyed each other. Such a thing really does not take place.
To explain this, it was believed that the law of electrodynamics failed in case of an atom in the
quantum world and the electrons move in different fixed orbits and do not emit energy as long as they revolve
in those fixed orbits. That was precisely what Bohr proposed in his model. Bohr blended the classical
planetary nature of electrons suggested by Rutherford with quantum theory of Planck to suggest a convincing
model of atoms.
Postulates of Bohr's model of atom

1. Quantization of energy levels:

Electrons revolve round the nucleus in fixed circular orbits called energy levels or shells designated
by the letters K, L, M, N, O ........ The first shell is the K shell, the second shell the L shell, the third M
shell and so on. The electron possesses the minimum energy when revolves in the K shell. The energy of
the electron goes on increasing as it revolves in higher and higher shells such as L, M, N, O.... In other words,
the energy of electron increases as its distance from the nucleus increases. These energy values are fixed.
This is otherwise called the energy levels are quantized.
2. No loss or gain of energy in a shell
As long as electron revolves round a particular orbit, the energy possessed by it is fixed. It neither
loses nor gains energy.
3. Absorption and emission of energy:
Electron can jump from one orbit to another. If the electron jumps from a lower orbit to a higher orbit,
it has to absorb energy. If the electron jumps from a higher orbit to lower orbit, it emits energy. These jumps
are called "quantum jumps" or "quantum leaps" as these jumps obey Planck's quantum theory.
Explanation for hydrogen atom:
There is one electron in hydrogen atom which usually revolves in the K shell. This is called the ground state
of hydrogen atom. All the other shells such as L, M, N, O... are also present in hydrogen atom. They are
vacant or empty. The electron can jump from the K shell to the L shell by absorbing appropriate amount of
energy. Similarly the electron can jump from the K shell directly to M shell while bypassing the L shell by
absorbing still greater but appropriate amount of energy. Likewise when the electron jumps back from M shell
to K shell it will emit or evolve energy equal in magnitude that it absorbed for jumping from K to M shell.
When electron is revolving in higher shells such as L, M, N, O etc., it is said to remain in the excited state.
As long as the electron remains in a particular orbit(shell), it neither emits nor absorbs energy. We say that
the energy levels are quantized which means that electron takes fixed or permitted energy values.
4. Planck's quantum theory for emission and absorption
The energy absorption and emission that takes place when electron jumps from one shell to another
occurs in the form of single packet or photon(quantum) according to Planck's Quantum theory.
Explanation:

E4
E3
E2
E1 (E2-E1) absorbed

N
M
L
K
(E3-E1) emitted

ENERGY LEVELS(SHELLS) OF HYDROGEN ATOM

E1, E2, E3..... are the energy of electron when it revolves in 1st, 2nd, 3rd.... shells respectively.
E1< E2 < E3 < ........ the energy values go on increasing as we go further away from the nucleus.
If the electron jumps from 1st(K) to 2nd shell(L), the energy difference is equal to ΔE=E2-E1. This differential
amount of energy has to be absorbed. According to the postulate of Bohr this absorption will take place in
the form of a single photon of energy selecting the particular frequency from the electromagnetic radiation
following Planck's quantum theory.

E = E2 - E1 = h1 = hc = hc1
1
ν1 is the frequency of the photon needed for the electron to jump from K shell to L shell. Now when the
electron will jump from L shell back to the K shell, it will emit the same amount of energy in the form of
a single photon having same frequency ν1. Similarly when electron jumps from 1st shell(K) to 3rds shell(M)
directly, then it has to absorb the differential amount of energy i.e (E3-E1)in form of a single photon having
a fixed frequency(ν2).

E' = E3 - E1 = h2 = hc = hc2

2
When it will jump from M shell back to K shell it will emit a photon having same frequency ν2.
SAQ 10:
(i) The electron in H atom jumps from 4th shell to 2nd shell. Will energy be absorbed or emitted?
(ii) The electron in H atom jumps from 3rd shell to 7th shell. Will energy be absorbed or emitted?
(iii) The energy of the electron in the different shells is as follows.
K shell= p joule, L shell = q joule, M shell= r joule, N shell = s joule
Answer the following questions.
(a)Can the electron in the hydrogen atom lose energy when it is revolving in the 2nd
shell(L)? If so by what amount and where will it go?
(b)Can the electron in the H atom lose energy when it revolves in the K shell? Give
reason.
(c)The electron is in the M shell. Can it lose energy? If so, by what amounts and where it can go
after losing energy?
(d)In which shell, the electron can absorb energy only but cannot lose energy?
Justify.
(e)The electron is present in the 4th shell(N) of H atom. How many possible photons
it can emit? Which jump will emit greatest energy photon and which the least energy
photon?
5. Quantization of angular momentum:
By virtue of the electron's motion in a circular orbit, it possesses angular momentum which is equal
to the product of mass of the electron, velocity of the electron and the radius of the orbit.
Angular Momentum = m × v × r
According to Bohr's postulate, the angular momentum of an electron takes fixed values like energy levels.
Thus the angular momentum of the electron is quantized and is expressed by a whole number multiple of
h/2π.

mvr= n h Where n= 1, 2, 3, and so on.

2
If n=1, the angular momentum = h/2π = angular momentum of electron in K shell
If n=2, the angular momentum = 2 × h/2π = angular momentum of electron in L shell
If n=3, the angular momentum = 3 × h/2π = angular momentum of electron in M shell and so on.

6. Energy of Electron in H atom:

Bohr derived mathematically the energy of electron in different shells of hydrogen atom or hydrogen like
species containing one electron. The energy equation is presented below in its simplest form.

2
kZ
E=
n2
(where Z = atomic number and k is a constant whose value is 2.18 × 10 -11 erg per atom or 2.18 ×10 -18
joule per atom or 13.6 eV per atom ( 1 eV = 1.602 × 10 -19 joule)
n= shell number or the principal quantum number i.e 1 for K shell, 2 for L shell, 3 for M shell and so on).
For H atom, Z=1, so the energy equation is
k
E=
n2
From the above relation, we can find the energy values of electron in the different shells.
E1 = - k, ( n=1) E2 = - k/4, (n=2)
E3 = - k/9, (n=3) E4 = - k/16, (n=4) and so on.
From this we can calculate the energy difference between any two shells and then using Planck's quantum
theory, we can calculate the frequency (or the wavelength or wavenumber) of the photon absorbed or emitted
for a particular jump.
Example: Calculate the wavelength of the photon to be absorbed by the electron in H atom to
jump from 1st to 2nd shell. To which region of the electromagnetic spectrum does this photon belong?
Solution: The energy of the electron in the 1st shell= E1 = - k
Energy of the electron in the 2nd shell =E2 = -k/4
So the energy difference =ΔE=E2 - E1= -k/4 - (-k) = 3k/4

According to Planck's Quantum theory, E = E2 - E1 = hc ⇒ hc = 3k

  4

 hc   .   erg. sec   cm / sec

⇒    .   cm  .      Å
k   .   erg

The electron will absorb a photon of wavelength 1216Å in order to jump from K shell to M shell. This wave
belong to the ultraviolet region of the electromagnetic spectrum
SAQ 11:
(i) Why is the energy of the electron is negative?
(ii) What will be the wavelength of the photon emitted when electron in H atom jumps from 2nd shell
to 1st shell?
(iii) Calculate the wavelength of the photon absorbed when electron in H atom jumps from 1st shell to
3rd shell. In which region of the electromagnetic spectrum does this belong.
(iv) Calculate the wavelength of the photon emitted when electron jumps from 3rd shell to 1st shell in
H atom.
(v) Calculate the wavelength of the photon absorbed when electron jumps from 2nd shell to 3rd shell.
To which region does it belong? What photon will be emitted when the electron jumps from 3rd shell back
to the 2nd shell?
(vi) What is the value of energy of electron in the 6th shell and 3rd shell in H atom? Which is of higher
energy? Answer in terms of the constant k(2.18 × 10-11erg).
(vii) When the electron jumps from 1st shell to infinite distance, how much energy is required? What is
the energy of the electron at the infinite distance?
(viii) Suppose in one H atom, the electron jumps from 2nd shell to 1st shell, in another H atom electron
jumps from 3rd shell to 1st shell and in the still another atom, electron jumps from 4th to 1st shell. How does
the wavelength vary in respect of the three photons emitted in the three jumps? Does it increase or decrease
in the sequence of the jumps given above?
(ix) Why the shells were designated as K, L, M, N ..... shells and not A, B, C, D,..... ?

DERIVATION FOR THE ENERGY OF ELECTRON

Bohr presumed that the electron was executing circular motion about the nucleus. This is due to the balance
of centripetal force(in this case coulombic force of attraction of the nuclues to the electron) and centrifugal
force
1 (Ze) e
Centripetal Force = Force of attraction = r2 (Coulomb's law)
4
2
Ze
= (1)
4 r 2
Where Z = nuclear charge(atomic number), e = charge of electron = charge of proton. and ε = permitivity
of the medium(constant), r = radius of the orbit
2
centrifugal force = m v (2)
r
where m = mass of the electron, v = velocity of electron.
Equating (1) and (2) we get
2 2 2
mv Ze mv =
2 Ze
= ⇒ (3)
r 4 r 2 4 r
2
2
v = Ze
⇒ (4)
4 m r
According to Bohr's postulate on quantization of angular momentum:
n2 h2
mvr= n h ⇒
2
v = (5)
2 42m2r 2
From equations (4) and (5) we get

Ze2 n2 h2 2 2
n h
= ⇒ r = (6)
4 m r 42m2r 2  m e2 Z
This gives the radius of the orbits K (n=1), L (n=2), M(n=3) ..... shells of H atom or H-like species containing
1 electron.
e = 1.602 ×10-19 coul, ε = permittivity of air = 8.85 × 10-12 coul2N-1m-2
h = 6.627 ×10-34 J.sec m = 9.1 × 10-31 Kg
Substituting all these values, equation (6) is reduced to:
-8 2 2
0.529X 10 X n 0.529 n
r = cm ⇒ r = A (7) (RADIUS OF ORBITS)
Z n Z
2
For H atom Z = 1, so radius equation is reduced to r = 0.529 n A (8)
n
Where n = 1, 2, 3,..... for 1st, 2nd, 3rd shells......... respectively.
SAQ 12: (a) Find the radii of K and L orbits of H-atoms.
(b) Find the radii of M, N orbits of He+ ion.
CALCULATION OF ENERGY
Total energy of electron = potential energy + kinetic energy
(Ze) e 2
E(potential) -= 1 1 Ze
4 r =- (9)
4 r
 E(kinetic) = ½ mv2 (10)
2 1 2
E(total) = 1 m v - Ze (11)
2 4 r
Substituting the value of mv2 from equation (3) in the above equation , we get
2
1 Z e2 1 Ze Ze2
E(t otal) = -
4 r =- 1 (12)
2 4 r 2 4 r
Substituting the value of r from equation (6) we get(after simplification)
4 2 2 4
mez kZ me
=- 22 2
= - (where k = 2 2 )
8n h n2 8 h
Substituting the values of m, e and ε we get the value of k.
k = 2.18 × 10-18 Joule/atom = 2.18 × 10-11 Erg/atom
__________________________________________________________________________________
[N.B: If you carry out the above calculations in CGS system, you have to take force of attraction(centripetal
Ze 2 1
force) according to Coulombs law as : F  (In CGS the constant in Coulombs law =1 which is
r2 4 0 in SI.
So the radius equation and energy equation will be as follows

n2h2 2 2 me 4 Z 2  2 2 me 4  Z 2
r E    2 ;
4 2 me 2Z n2h2 2
 h n
2 2 me 4
k 2
 2.18  10 11 Erg / atom ]
h
__________________________________________________________________________________
The energy of electron in H or H-like species containing one electron is given by the following equation.
2
kZ
E = - (k = 2.18 × 10-18 J/atom = 2.18 × 10-11 E/atom)
n2
For H atom Z=1, the equation for energy is reduced to
k
E = - ( where n = 1, 2, 3...... for the K, L, M.... shells respctively)
n2
Value of k in eV (electron volt):
1 eV = 1.602 ×10-5 Joule, k = 2.18 ×10-18 J = 13.6 eV
Value of k in KCals/mole:
k = 2.18 × 10-18 × 6.023 ×1023 ≈ 1313 KJ/mole = 1313/4.2 ≈ 313 KCals/mole
VELOCITY OF ELECTRON IN BOHR'S ORBIT
From Bohr's postulate we know that
h nh
m v r =n ⇒ v=
2 2mr
Substituting the value of r(radius) from equation (6) and on simplification we get
e Z
v = Substituting the values of the constants we get
2 h n
6 8
v = 2.18 X 10 Zn m/s = 2.18 X 10 Z
n
cm/s
SAQ 13 : Calculate the velocity of electron in (a) 1st orbit of H-atom (b) 2nd orbit of He+
SAQ 13 (a): Between H and D(deuterium atom), both having Z =1, in which case the ionisation energy ( 'k' value)
is greater ? Or they have same ionisation energy ?
Answer: D has a greater 'k' value and hence ionisation energy. The presence of a neturon in the nucleus in D
makes the nuclear pull greater and hence the difference.
Origin of Hydrogen Spectrum:
The energy profile in H atom is given below. The energy values of electrons go on increasing as we move
to higher shells. The 1st shell has energy -k, the 2nd shell -k/4, the 3rd shell -k/9 and so on.
 k
P
O k-
- 25 36

N - k16
7k
- k9
144
M
5k
36

L - k
4

3k
4

K -k
(Energy Profile for the different shells in H atom)

If we calculate the gaps between the successive energy levels, we find that the energy gap between two
successive shells gradually decreases as we move to higher and higher shells and after a few shells the gap
becomes very close to zero. That means, the electrons possesses nearly equal energy values as we move
to higher shells. Now let us know the origin of hydrogen spectrum.
A glass tube containing hydrogen gas contains thousands and thousands of H atoms. When the gas is
subjected to high voltage at low pressure, the only one electron present in the K shell(ground state) jumps
to different higher shells in different atoms. In some atom, the electron jumps from 1st to 2nd, in some other
atom from 1st to 3rd, and in other atom from 1st to 4th and so on. This takes place by absorbing photons
of different energy available to it when it is subjected to high voltage. These are called the excited H atoms
in which electrons are present in different higher energy levels in different atoms. Note that each atom
contains only one electron but present in different higher shells in different atoms. After some time the
electrons will like to come back from different higher energy levels present in different atoms to different
lower energy levels in the respective atoms. In these processes photons of different energies are emitted.
When this mixture of photons emitted is passed through a prism, the radiations get dispersed to give the
spectrum on the photographic plate. The spectrum consists of several series of lines that have been named
as Lyman series, Balmer series, Paschen series, Brackett series, Pfund series and Humphreys after
the scientists who had discovered them. Say for example, all the lines observed in the Lyman series are due
to transition of electrons from different higher shells to the first shell and the lines of Balmer series are due
to transitions from different higher shells to the 2nd shell and so on. Note that only because the electrons
can take up fixed energy levels(K,L,M,N....) and not any energy level or all possible energy levels, we get
discrete and fixed lines in each series of H spectrum and get a discontinuous spectrum. Each particular
transition(say 3rd shell to 2nd shell) gives rise to one line in the spectrum. Had electron assumed all possible
energy levels, it would have jumped to infinite number of energy levels and hence emitted infinite number
of radiations which would have resulted in a band or continuous spectrum like solar spectrum. But such a
thing does not really take place. We get discontinuous spectrum consisting of a few discrete lines in each
series. This clearly proved the validity of the Bohr's postulate of atomic structure that the atom consists of
some fixed number of shells having fixed energy values. In fact, Bohr took the idea of fixed orbits only from
the experimental finding of the H spectrum by Balmer, the first scientist to observe the H spectrum.
Why the lines in each series of spectrum come close to each other and finally merge onto one other
to form a continuum?
This is because of the following reason.Since the gaps between successive energy levels diminish(as shown
before in the energy profile) and gradually tend to become zero, the energy difference between a fixed lower
shell and the variable higher shells tend to approach close to each other. Their transition energies also tend
to approach close to each other. Therefore the lines in each spectral series also approach closer as we move
on to lower wavelength region and after a few discrete lines, they merge onto one another and stop further
exetension forming the continuum.
DERIVATION OF RITZ EQUATION FOR HYDROGEN SPECTRUM
2
kZ
E = - (energy of electron)
n2
Let n1 = principal quantum number of any lower shell and n2= principal quantum number of any higher shell,
2 2
-kZ -kZ
E1 = and E 2 = n 2
n2
1 2
 2 2
-kZ -
2
-kZ 1 1
 E = E2 - E1 = = kZ 2 - n 2
So
n 22 n2 n1
2
1

Applying Planck's quantum theory we get

2
1 1
kZ 2 -
E  hc So,  =
hc n 1 n 2
2

2 1 - 1
 = RZ
n2 n2 (RITZ EQUATION)
1 2
(where R = k/(hc) = Rydberg constant = 109677 cm-1 = 1.09677 × 107 m-1
FREQUENCY EQUATION:
2 2
1 - 1 1 - 1
h = k Z n2 n2 ⇒  = kZ n2 n2
1 2 h 1 2

15 2 1 - 1
 = 3.29 X 10 X Z n2 n2 sec -1
1 2
(where ν is the frequency of the radiation and k/h = 3.29 × 1015 sec-1)
Example: Find the wavelength of em radiation emitted when electron jumps from 4th shell to 1st shell in H atom.
To which region of the em spectrum does it belong?
1 - 1 16
 =1 =
Solution:  = 109677 cm -1 12 4
2  X -8
15 X 109677 = 972.5 10 cm
⇒

λ = 972.5 Å
The radiaton falls in the UV region.
Example: Calculate the frequency of radiation emitted electron jumps from 3rd to 2nd Bohr's orbit in He+ ion.
15 2 1 - 1
Solution:  = 3.29 X 10 X 2 sec -1 (since Z=2 for He+)
22 32
ν = 1.8 × 1015 sec-1
(We can also first calculate wave number from Ritz equation and then find the frequency)
SAQ 14:
(a) Calculate the wavelength of radiation required to be absorbed by He+ for the electron to jump from 1st to 3rd
orbit. To which region of the em spectrum does it belong?
(b) Calculate the frequency of radiation emitted when electron jumps from 3rd to 2nd shell in Li2+ ion.

5
Balmer Series 4
3
2 2
1
Lyman Series

Bracket Series 4
3
5
6 4
5 Paschen Series
6

Transitions of Electrons giving Different Series in H-Spectrum

1. LYMAN SERIES:
(i) This series of lines falls in the ultraviolet region of the electromagnetic spectrum.
(ii) The different lines appear due to the transition of electrons from various higher energy
levels in various H atoms to the 1st shell.
The transition : 2nd shell to 1st shell gives the → 1st line
3rd shell to 1st shell gives the → 2nd line
4th shell to 1st shell gives the → 3rd line and so on.
If n1= any lower shell and n2 = any higher shell, then we can say that for Lyman series:
n1 = 1 and n2 = 2, 3, 4, 5..........
2. BALMER SERIES:
(i) This series falls in the visible region of the electromagnetic spectrum.
(ii) The different lines in this series are due to the transition of electrons from various
higher energy levels in various H atoms to the 2nd shell.
For Balmer series: n1= 2 and n2 = 3, 4, 5, 6..........
So 1st line → the transition from 3rd shell to 2nd shell
2nd line → the transition from 4th shell to 2nd shell
3rd line → the transition from 5th shell to 2nd shell and so on.
3. PASCHEN SERIES:
(i) This series appears in the first part of the infrared(IR) region of the electromagnetic spectrum.
(ii) The different lines in this series are due to the transitions of electrons from various higher energy
levels in various H atoms to the 3rd shell.
For Paschen series: n1= 3 and n2 = 4, 5, 6, 7 .......
So 1st line → the transition from 4th shell to 3rd shell.
2nd line → the transition from 5th shell to 3rd shell.
3rd line → the transition from 6th shell to 3rd shell and so on.
4. BRACKETT SERIES:
(i) The lines appear also in the IR region but in higher wavelength region.
(ii) The different lines in this series appear due to the transitions of electrons from various higher energy
levels in various H atoms to the 4th shell.
For Paschen series: n1= 4 and n2 = 5, 6, 7, 8 .......
5. PFUND SERIES:
(i) The lines appear also in the IR region but still at higher wavelength region.
(ii) The different lines in this series are due to the transitions of electrons from various higher energy
levels in various H atoms to the 5th shell.
For Paschen series: n1= 5 and n2 = 6, 7, 8, 9 .......
6. HUMPHREYS SERIES
(i) The lines appear also in the IR region but still at higher wavelength region.
(ii) The different lines in this series are due to the transitions of electrons from various higher energy
levels in various H atoms to the 6th shell.
For Paschen series: n1= 6 and n2 = 7, 8, 9 ...
SAQ 15:
(i) Indicate to which transitions the following lines of each series in H spectrum represents.
(a)) 2nd line of Balmer series (b)1st line of Lyman series (c)3rd line of the
Paschen series (d)3rd line of the Lyman series(e)3rd line of Balmer series
(f)2nd line of the Bracket series (g)1st line of the Pfund series
(ii) Calculate the wavelength of the 2nd line of the Lyman series. Check whether it belongs to UV region
or not.
(iii) Calculate the wavelength of the 3rd line of Balmer series. Check whether it belongs to visible region
or not.
(iv) Calculate the wavelength of the 2nd line of Paschen series and check whether it falls in the IR region
or not.
(v) Predict what would have been the nature of H spectrum, if the electrons would have taken all
possible orbits(infinite number) instead of some fixed energy levels. What is the actual nature of H spectrum.
Merits of Bohr's Model of Atom:
Bohr's postulates and mathematical derivation of energy of electron could satisfy the experimental finding of
the hydrogen spectrum. The actual wavelengths of the spectral lines could match well with the mathematical
calculation based on Bohr's theory. That became the greatest success of the Bohr's theory.
Demerits of Bohr's Model of Atom:
1. Bohr's theory satisfactorily explained the spectra of H and H like species which contain one electron
such as He+, Li2+ etc. It failed to explain the spectra of species containing more than one electron such as
He, Li etc.
2. When powerful spectrometers(spectrometers having high resolving power) were discovered, it was
found that each line of the hydrogen spectrum was split into two finer lines called a doublet. This splitting
of spectral lines could not be explained by Bohr's theory.
Note that it was subsequently revealed that each shell consists of a fixed number of subshells. The subshells
belonging to a particular shell in H or H like species possess equal energy values. Again each subshell was
found to contain a few orbitals and each orbital can accommodate two electrons with opposite spin. If one
electron spins clockwise the other spins anticlockwise and the two states vary slightly in their energy values.
Hence two different transitional energies differing slightly in their energy values are emitted when electron
jump from a particular higher energy level to the fixed lower energy level. Thus a single line is split into two
finer lines(doublet). Sommerfeld modified Bohr's theory and suggested the presence of subshells by using
the concept of elliptical orbits. But his theory could not become popular due to advent of wave mechanical
approach to atom.
3. When the spectrum was taken in the presence of external magnetic field or electric field, it was found
that each spectral line is split into some finer lines.These were called the Zeeman effect and Stark effect
respectively. Bohr's theory could not explain these effects(The explanation for these effects are given later).
4. It was suggested by de Broglie that electron moves in the form of a wave and not in the conventional
circular motion as was commonly believed. He proved beyond any doubt that electron in each energy level
moves like a standing wave. It has a wavelength, frequency and a wavenumber. This is called electron wave
which is a matter wave and is different from electromagnetic waves. Bohr's theory could not explain this
wave nature of electron.
5. Heisenberg proved that it is not possible to accurately know the position and velocity of very
tiny(microscopic)particles like electron. So it is wrong to say that electrons are rotating in fixed orbits about
the nucleus. This was a major challenge to Bohr's theory. While Bohr suggested that the electrons move in
fixed orbits(K,L,M,N...) having fixed radii and energy levels, it was found subsequently to be untrue. The
electrons do move in fixed energy levels in agreement with Bohr's theory, but not in fixed orbits. The term
'orbit' therefore was replaced by another term 'orbital'. Orbital is a three dimensional space(and not a
two dimensional circular path which is called the orbit)about the nucleus which possesses fixed energy
and the electron moves around the nucleus anywhere inside this space. The electron does not repeat its
motion again and again in the same track or orbit as suggested by Bohr's theory. It remains within the
boundary of an orbital and rotates inside anywhere and everywhere as a wave.
6. Bohr did not give any logic to his postulate of quantization of angular momentum(mvr = nh/2π)
although it was later found to be true by de Broglie's theory of matter waves. It was merely a mathematical
necessity at that time.
7. Bohr's theory could not explain the shape of molecules.
SAQ 16: Define the term, 'orbital' and distinguish between orbit and orbital.

Quantum Mechanics
The Planck's quantum theory coupled with Bohr's theory could not explain many observable quantities about
the structure of atom. Quantum mechanics(wave mechanics) was introduced to explain these quantities. The
central idea behind wave mechanics is that electron is not merely a particle but also a wave.
MATTER WAVES & DE BROGLIE'S EQUATION
In 1924 French Physicist Louis de Broglie predicted that like electromagnetic radiations, material particles
carrying mass and moving with a velocity should behave like a wave, which is the reverse phenomenon of
Planck's quantum theory. These are called matter waves.
Derivation of de Broglie's equation:
De Broglie used Einstein's equation for material particle( E = mc2) and Planck's quantum theory used
for electromagnetic waves( E = hc/λ) to find the wave length of matter waves.
E = m c2 (1) Einstein's equation
E = (hc)/λ (2) Planck's quantum theory
From equations (1) and (2) we get
mc2 = hc/λ ⇒ λ = h/mc
Replacing 'c' (velocity of light) by velocity of the material particle 'v' which is variable we get.

h h
=mv = p where p = momentum of the particle = m × v
Validity of de Broglie's equation:
(1) Macroscopic particles: For macroscopic or big particles the de Broglie wavelenght is negligibly small
compared to their dimensions(sizes). So the wave nature of such particles cannot be detected by any
experimental technique. Therefore matter waves are believed to be non-existent for macroscopic particles.
(2) Subatomic and atomic particles (microscopic particles): Subatomic particles like electrons, protons,
neutrons etc and atomic particles like H, He etc.moving with high speed, the de Broglie wavelengths are
comparable or greater than their dimensions. Hence the wave nature of such particles could be detectable
and hence are important.
Example: (a) Calculate the wavelength of a ball weighing 5 g and moving at a speed of 108 cm/sec.
(b) Calculate the wavelenght of an electron which is moving at a speed of 108 cm/sec.
h 6.627 X10 -27 erg.sec
Solution: (a) =mv = = 1.325 X 10-35 cm = 1.325 X 10-27 A
5 g X 108 cm/sec
Since this wavelenght is negligibly small compared to the size of a ball(same for any macroscopic particle),
the wave nature of such particle is not detectable.
h 6.627X 10-27 erg.sec
(b) =mv = = 7.28 10-8 cm = 7.28 A
-28 8
9.1 10 g 10 cm/sec
X X
This wavelength is greater than the size of electron as electron is a point mass having negligilbe size.
Therefore the wavelength of electron is detectable. Other microscopic particles also behave in the similar
manner.
Relationship between de Broglie wavelength of matter waves and kinetic energy of the particle:

h h2 h
=mv = =
m2 v2 2 m Ek So λ ∝ 1/√Εκ

SAQ 17: Indicate which one is a matter wave and which a electromagnetic wave?
α- rays, γ- rays, cathode rays, moving bullet, x-rays, neutron beam, IR-rays.
Verification of de Broglie equation: (Electron diffraction experiment):
Wave nature of matter waves was verified by Davission and Germer by their famous electron diffraction
experiment. Interference and diffraction are two properties of all electromagnetic waves. The same properties
were observed for electron beam.
The diffraction phenomenon was known for light and other electromagnetic waves such as x-rays. When a
x-rays beam was allowed to strike on pure metallic crystal(say Nickel), the rays were reflected from different
parallel crystallographic planes and produce a typical pattern in photographic plate which consisted of alternate
bright and dark regions(rings). This is called x-ray diffraction pattern. This is due to interfence of waves
giving bright regions for constructive interference and dark regions for destructive interferene. When electron
beam(cathode rays) was used in place of x-rays, similar type of diffraction pattern(analogous to x-rays
diffraction) was observed. This confirmed the wave nature of moving electron.
Note that like electron diffraction, neutron diffraction has also been observed in recent years.
(3) Validity of quantization of angualr momentum:

(a) Regular Standing wave (b) Wave out-of-phae

(In-phase)

n=3 n=4 n= 5 n =6

Let us imagine that an electron is moving in a Bohr's orbit in the form of a wave having wavelength λ. This
wave behaves like a standing or stationary wave which remains in phase i.e repeats the same distance and
same phase in the same time interval. This is possible if the two ends of the electron wave meet in the same
phase to give an unbroken and regular series of crests and troughs. An integral number(1,2, 3...) number of
waves fit round the orbit in order to become a standing wave. If the wave goes out of phase the wave soon
dies down. In order to have a standing wave, it is necessary that the circumference of the cicle(2πr) which
is the the path length of the electron in one rotation should be a whole number multiple of wavelength(λ.).
2πr = n λ (where n = a whole number)
Substituting the value of λ from de Broglie's equation we have
2πr = n.( h/mv) ⇒ mvr = n (h/2π)
This is a postulate of Bohr's atomic model(quantization of angular momentum) which is validated by de
Broglie's concept of matter waves.
SAQ 18: Calculate the wavelength of electron in the (a) 2nd Bohr's orbit of hydrogen atom and (b) 3rd
Bohr's orbit of He+ ion.
SAQ 19: Calculate the wavelength of neutron moving with a velocity of 1.5 × 109 cm/sec.
SAQ 20: Draw the wave fronts of electron wave in n=1, n=2, n=3 and n=3 shells.

Distinction between matter waves and em waves.

1. EM waves are associated with electric and magnetic field perpendicular to each other and to the direction
of propagation of wave.
Matter waves may or may not be associated with any electric or magnetic field. For example, a moving
neutron or bullet are not associated with any field while a moving electron, proton or α- particle is associated
with magnetic field.
2. EM waves do not carry any mass. But matter wave is made up of material particles which carry mass.
3. All EM waves move with same velocity(3×1010 cm/sec). But matter waves travel with different velocities
which cannot usually exceed the velocity of light.
4. The wavelengths of EM waves are calculated from λ = c/ν. But the wavelength of matter waves is
calculatd from de Broglies' equation λ = h/(mv).
HEISENBERG UNCERTAINTY PRINCIPLE(HUP)
The precise prediction of path of a moving body requires that both the position and velocity(hence momentum)
be known accurately at any given time. For a macroscopic particle like a cricket ball it is possible but for
a microscopic particle like electron, proton etc. there will always be an error or indeterminancy or imprecision
in the measurement of both these quantities. This is because the microscopic particles exhibit pronounced
wave nature(explained by de Broglie) while the macroscopic particles do not. Heisenberg proposed as the
first principle of quantum mechanics that there is always an inderminancy or error or uncertainty in the
measurement of observable quantities for subatomic particles belonging to the quantum world despite 100%
accuracy in the instrumental technique adopted for the purpose. He established a special and quantifiable
relationship between two pairs of variables what he said "cannonically conjugate variables". They are
(a) position and momentum of a particle
(b)energy possessed by the particle(E) and time(t) spent by the particle with energy E.
Definition of HUP: The simultaneous measurement of two cannonically conjugate variables(such as position
and momentum or energy and time) cannot be done precisely for a subatomic microscopic particle.
The more precise the measurement of position, the more imprecise is the measurement of momentum(mv)
and vice versa. Similarly more precise the measurement of energy(E) the more imprecise is the mesurement
of time(t) and vice versa. In no case, any variable can be measured with absolute precision(100% precision).
The imprecision in the measurement can be made very small(close to zero) but not equal to zero.
Mathematicaly HUP is expressed as follows:
Let Δx = uncertainty or imprecision or error in the measurement of position
Δp = m(Δv) = uncertainty or imprecision or error in the measurement of momentum
where m = mass of the particle and Δv = error in the measurement of velocity. According to HUP

Δx × Δp ≥ h/4π ΔE × Δt ≥ h/4π

Where ΔE = uncertainty in measurement in energy and Δt = uncertainty in the measurement of time.

Physical interpretation:
If Δx is made very small(Δx→ 0) i.e the position can be measured almost precisely, then Δp becomes
very large. This means that the imprecision in the measurement of momentum (hence velocity )of the particle
is very large. Similarly if Δp is made very small(Δp→ 0), i,e momentum(hence veolcity) can be measured
almost precisely, then Δx becomes very large. This means that the imprecision in the measurement of position
is very large.
Thought experiment
Whenever one makes some measurement by observing a particle it cannot be done without disturbing the
particle.
To view a moving electron let us use a hypothetical microscope. A light photon must strike onto the moving
particle and get reflected and enter the microscope eye piece, so that we can observe the particle. The impact
of a light photon onto the tiny electron will definitely disturb both its position and momentum. Since the
wavelength of bombarding photon is often greater or comparable with the size of the particle(electron),
phenomenon of reflection does not occur in this case. In stead the light is scattered after transferring a part
of its energy to the particle(Compton Scattering). Thus both position and velocity(hence momentum) of the
particle get altered. The electron will be recoiled to a different position and possess a different velocity. This
gives rise to the error or uncertainty in the measurement of both the parameters. According to HUP, the
product of the uncertainty of postion(Δx) and uncertainty of momentum(Δp) is nearly a constant. If one is
measured with more precision, then the other is measured with less precision.
Derivation of HUP:
According to principle of wave optics, the error or uncertainty in measurement of position of a particle(Δx)
by using a radiation having wavelength(λ) is approximately equal to λ.
Δx ≈ λ (1)
According to de Broglie's equation, λ = h/mv ⇒ mv = h/λ (2)
Heisenberg presumed that the error in velocity masurement(Δv) would be equal to or exceed the absolute
velocity(v) i.e Δv ≥ v Substituting the Δv for v in equation (2), we get
m × Δv ≥ h/λ ⇒ Δp ≥ h/λ (3) ( where Δp = uncertainty in momentum)
Substituting the value of λ from equation (1), we get
Δp ≥ h/Δx ⇒ Δp × Δx ≥ h
Subsequent refinement in the calculation has lead to the following Heisenberg equation
Δp × Δx ≥ h/4π
Validity of HUP by γ-ray Thought Experiment:
If we use a γ-photon to view a moving electron, the position can be measured more precisely as the
wavelenth(λ) of a γ-photon is small(λ = Δx). But since the photon carries more energy it will transfer more
energy to the electron upon impact and hence the measurement of momentum will be highly imprecise. On
the other hand, if we use a microwave photon to view a moving electron, the position measurement will be
more imprecise as λ for such a photon is large. But since it will transfer less energy to the electron, the
momentum measurement will be more precise.
NB: Note that these are not real experiments, in stead are thought experiment devised to explain HUP.
Consequence of HUP:
Since according to HUP, it is impossible to predict the position and velocity of electron with 100% accuracy,
we cannot say that electrons revolves round the nucleus in fixed circular orbits. We can speak always in
terms of probability. Thus Bohr's concept of 'orbit' was rejected and was replaced by the term 'orbital'.
Orbital thus was defined as the three dimensional space surrounding the nucleus in which the probability
of finding the electron possessing a particular energy value is maximum(>90%). Hence electron was
regarded as a standing wave. Besides its particle nature, it also has the wave nature. Since electron concept
is more abstract and mathematical, it is really difficult to imagine and interpret the acutal situation. To place
it most logically, the electron is believed to be smeared into a wave front that surrounds the nucleus like a
cloud with a fluctuating electron density. The density in the electron cloud is maximum at a particular radial
distance from the nucleus which is analogous to Bohr's radius in the classical quantum theory.
Example: The velocity of an electron in the 3rd shell of H atom is measured with 99% accuracy. Find the
uncertainty of postion.
Solution: The velocity of electron in the 3rd shell = 2.18 × 108 (1/3) cm/s
The error or uncertainty in velocity = 1% of velocity = 0.01 × 2.18 × 108 (1/3) cm/s = Δv
Δp = m × Δv (mass of electron = 9.1 × 10-28 g
Δx × Δp = h/4π ⇒ Δx × m Δv = h/4π ⇒ Δx = 7.9 × 10-7 cm = 79 Å
SAQ 21: The uncertainty in position of a moving proton was found to be 1 Å at certain moment. Calculate
the uncertainty in velocity at that moment.
Note that from HUP we can calculate that the probability of finding electron inside the nucleus of an atom
is almost zero.
Uncertainty of Energy and Time:
h
E  t  (1)
4
ΔE = uncertainty in measuring energy and Δt = uncertainty in measuring time
Derivation: Let the uncertainty in position is Δx and it has velocity 'v', then uncertainty in time Δt is
x
t  (2),
v
h h
But from momentum-position, we have p   x  (3)
4x 4p
h
Substituting the value of Δx in equn (2) we have, t  (4)
4pv
p2 dE p
Since E    v (5)
2m dp m
dE
 dp  v  dp   dE  v   dp  E  v  p (6)
dp
h
Combining equations (4) and (6), we get E  t 
4
Physical Interpretation: It implies that if a system can exist in a certain state(say in an excited state) for
a period not longer than Δt, the energy of the system will be uncertain by at least ΔE =h/(4πΔt).
For example, if an electron stays for about 10–8 s in an excited state before it returns back(emitting energy),
then energy of excited state can be determined with an uncertainty of
h 6.627  10 34 Js
E    5.276  10 27 J
4t 4  3.14  10 8 s

This has great importance in the spectroscopy. Since E  h  hc ,

Δ  or Δ  is called the 'line width" of the spectrum corresponding to that particular excitation. Usually line
width is exressed in terms of wave number i.e Δ 
If Δt = ∞, ΔE = 0. This becomes a stationary state(for example K shell of H atom).
SAQ: Calculate the width of the spectral line resulting when an atom in an excited state having
life time of 10–10 s returns to the ground state.
Solution: NB. For most calculations, we take ΔE ×Δt = h; (Not h/4π)
E h 1
E  hc      10  33.33m 1  0.33cm 1
hc thc 10  3 10 8

So the line width of the said emission is 0.33 cm–1.

Quantum Numbers:
There are four index numbers which give the complete information about an electron, such as: in which shell
the electron is present, in which sub-shell it is present, in which orbital it is present, what is its spin and what
is its energy value etc. Three of the quantum numbers(n, l and m) have resulted from the solution of the
Schrodinger's wave equation. If you want to learn more on Schrodinger equation and it solution, you
please read a special chapter on Schrodinger equation given in this e-conept of chemistry. The fourth
quantum number called spin quantum number(s) has come from spectroscopic studies. When all the four
quantum numbers n, l, m and s are assigned to any electron, the complete identity of the electron is revealed.
1. Principal Quantum Number(n):
(i)It represents the principal energy level or shell that we studied in Bohr's theory. It takes whole
number values 1, 2, 3...... representing the main energy levels.
n=1 stands for the 1st or the K shell
n=2 stands for the 2nd or the L shell
n=3 stands for the 3rd or the M shell
n=4 stands for the 4th or the N shell and so on.
This Q.N has resulted from the solution of R(r) - radial function of the Schrodinger wave eqaution.
(ii)It tells about the distance of the electron with respect to nucleus. If n is larger, the electron is
situated farther away from the nucleus and if n is smaller it is located closer to the nucleus. The radial
distance at which there is maximum probability of finding the electron in an orbital can be calculated by using
the Bohr's theory(same as Bohr's radius).
rn = 0.529 n2/Z Å
(iii)It determines the average energy value of the electron according to Bohr's theory, E= - kZ2/n2
The energy of the electron increases as we move to higher shells. E1 < E2 < E3 < E4 < so on
(iv) The maximum number of electrons that can be accommodated in a shell can be know from the
2n2 rule.
2. Oribital Quantum Number/ Azimuthal Quantum Number(l):
This is also called the subsidiary quantum number or angular momentum quantum number or
orbital quantum number. This Q.N has come from the solution of P( θ)-angular function(Legender
Function) of Schrodinger equation.
(i)It suggests that each shell is divided into a fixed number sub-shells.
(ii)It takes values 0,1,2...... upto (n-1), where n= principal quantum number.
The number of subshells present in a particular shell is equal to the number of l values that the shell
can have. This is dependent on the principal quantum number of the shell. The number of l values and hence
number of subshells is equal to the n value, the principal quantum number.
1st shell(K shell):
For n=1
l=0 (s-subshell)
(there is only one l value and thus 1st shell has one subshell called the s-subshell)
2nd shell(L shell):
For n=2
l = 0 and (s-subshell)
=1 (p- subshell)
Thus there are two values of l and the 2nd shell has two subshells namely s-subshell(l=0)
and p-subshell(l=1).
3rd shell(M shell):
For n= 3
l =0 (s-subshell)
= 1 (p-subshell)
= 2 (d-subshell)
Thus there are three values of l and 3rd shell has three subshells namely s-subshell(l=0), p-subshell(l=1)
and d-subshell(l=2).
4th shell (N shell):
For n=4
l=0 (s-subshell)
=1 (p-subshell)
=2 (d-subshell)
=3 (f-subshell)
Thus there are four values of l and the 4th shell has four subshells namely s-subshell(l=0), p-subshell(l=1),
d-subshell(l-2) and f-subshell(l=3).
Similarly the 5th shell has five subshells(s, p, d, f, g), 6th shell has six subshells and so on.
Note that s, p, d and f stand for the terms 'sharp', 'principal', 'diffused' and 'fundamental' respectively
derivied from spectroscopic studies.
SAQ22:
(a) What is the value of l for a p-subshell ?
(b) How many subshells are there for the 3rd shell. What are their l values and what subshell does each
represent?
(c) An electron is present in the 2nd shell and in the p-subshell. Assign the n(principal quantum number)
and l(azimuthal quantum number) to the electron.
(d) An electron has quantum numbers as follows: n= 4 and l=3, In which shell and which subshell it is
present.
(e) How will you distinguish between a p subshell of 2nd shell and p subshell of the 3rd shell? Are they
same? Explain.
(f) An electron is present in the 5th shell and s-subshell. Assign the n and l values.
(g) One electron is present in the f-subshell of 4th shell and another electron is present in the f-subshell
of 5th shell. How can you distinguish between the two electrons?
(h) How many subshells does the 5th shell(n=5) have? What are their l values and symbols representing
them.

(iii) The value of l tells about the shape of an orbital. Although magnetic quantum number speaks about
the presence of orbitals, their shapes are known from the l value.
s-orbital(l=0) spherically symmetrical p-orbital:(l=1) dumbbell shaped(2 lobes)
d-orbital:(l=2) double dumbbell shaped or four lobes (discussed later)
f-orbital:(l=3) complex (discussed later)

pz
py

px
(p-orbitals shown together)
(spherically symmetrical s-orbital)

px py pz

(dumbbell shaped p-orbitals shown separtely)

When l value of electron is known to be 0, immediately we know that it is s-orbital and its shape is spherically
symmetrical. Similarly, if the l value is 1, it is a p-orbital and its shape is dumbbell shaped. Similarly when
l=2, it is d-orbital and is double dumbbell shaped. Note that the s-obrital of 1st shell, 2nd shell, 3rd shell and
any other shell have the same l value(0), they have the same shapes(spherically symmetrical) but they differ
in size. As the n value increases the sizes go on increasing. Similarly p- orbitals belonging to 2nd, 3rd, 4th
and any other higher shell are of same shape(dumb bell) but they differ in size. Same consideration can be
extended to d and f orbitals.
(iv) In a given shell, the order of energy among the subshells is as follows:
s<p<d<f
For example, in the 4th shell, which contains all the four subshells s, p, d and f, the 4s subshell possesses
the least energy while 4f subshell possesses the greatest energy and the
order is: 4s<4p<4d<4f.
Note that we should not compare a 4s subshell with a 3p subshell or a 3d subshell with a 4p subshell and
so on. For comparison, the subshells of the same shell is considered. s-subshell is spherically symmetrical in
shape and it is most tightly bound to the nucleus. In other words, the nucleus attracts the s-subshell to the
maximum extent and for that reason, it possesses the minimum energy. This is called the penetration power
of an orbital. This is maximum for the s- orbital and as we move from s to p and then to d and finally to
f- subshells, the subshells become less and less tightly bound to the nucleus and the penetration power
decreases in the same order. This is because their shapes are not spherically symmetrical. They have
dumbbell shape for p-subshell, double dumbbell shpaed for d orbitals and more compliated shapes for f-
subshells. They become more and more diffused. The nuclear attraction, thus, gradually falls in the same
order. Hence the energy of subshell increases in the order cited above. Note that this order of energy is valid
only when there are electrons in these orbitals. For H or H like species, all the subshells belonging to a
particular shell possess the same energy.
4s = 4p = 4d = 4f (for H atom)
SAQ 23:
(a) Give the decreasing order of energy for the sub-shells present in the 2nd shell.
(b) Is the order correct. 3s>3p>3d? Explain.
(c) Between 4p and 4f which has higher energy?
(d) An electron has n=4 and l=1. Where is it located?
(e) Can an elenctron have n=2 and l=2? Justify.
(f) Between 2s and 2p subshell which is of higher energy?

(v) Subshell remaining constant, if the principal quantum number increases the energy of the electron
increases.
1s < 2s < 3s < 4s < ..... 2p < 3p < 4p < 5p < .....
3d < 4d < 5d < 6d < ..... 4f < 5f < 6f < ......
This is because the energy of electron is mainly dependent on the 'n' value (E = -kZ2/n2)
(vi) Orbital angular momentum: The electron in an orbital has an angular momentum expressed by

h
h
Angular momentum = l ( l + 1) (where h/2π = )
2
Note that the above expression for angular momentum is used in wave mechanics to find the magnetic
moment of orbital and hence its interaction with external magnetic field. The angular mometum from
Bohr's classical theory(mvr = nh/2π) is used for calculating energy of electron.
Due to angular momentum, an orbital is associated with orbital magnetic moment(μL) which is expressed by
e
L = X angular momentum
2mc
eh -14
= l ( l + 1) = 9.27X 10 l ( l + 1) J
4mc

3. Magnetic Quantum Number(m):

(i) It suggests that each subshell is further subdivided into a fixed number of orbitals. From the l value
we know the presence of subshells in a shell while from m value we know the presence of orbitals in a
subshell. 'm' values are the result of the solution of F(φ)- angular function of the Schrodinger equation.
(ii) The number of m values depends on l value, that means the subshell determines how many orbitals
it can possess. As many m values are possible for a given subshell, same number of orbitals it will have.
A subshell can have (2l+1) values of m, and so it will contain (2l+1) number of orbitals. For example
s-subshell: l=0: (2l+1)= 0+1 = 1, So s-subshell has one orbital which is called the s-orbital. This
means that the s-subshell itself is the s-orbital
p-subshell: l=1: (2l+1)=2+1=3, So p-subshell has three orbitals which are designated as px, py and pz
orbitals.
d-subshell: l=2: (2l+1)=4+1=5, So d-subshell has five orbitals which are designated as dx2-y2, dz2, dxy,
dyz and dzx.
f-subshell: l=3: (2l+1)=6+1=7, So f-subshell has seven orbitals which are designated as fxz2, fyz2, fxyz,
fz(x2-y2),, fx(x2-3y2) fy(3x2-y2) and fz3

(iii) m takes values -l, -l+1, -l+2.......0, 1, 2.........+l ( 2l + 1 values)

In the previous point we knew how many values of m are possible for a given l value. Here we know what
values, m can take. m can take values from -l to +l through 0. Each successive value is obtained by adding
1 to the previous value.
l=0(s-subshell):
m=0 (one value stands for the one s-orbital)
l=1(p-subshell)
m=
-1
p 0 p & p (three values for the three p orbitals px, py and pz . m = ± 1 can
z x y
+1
be interchangeably used for px and py)

l=2(d-subshell)
m =
-2
-1
d y z d zx 0 d d 2 2 d xy (five values for the five d orbitals)
+1 z2 x - y
+2
 l=3(f-subshell)

f f 2
m= xz
2
yz
-3
-2
-1 f 2 2
f xy z f 2 2
0 f 2 - 2y
x ( x - 3y ) / y(3x
z(x - y ) f 3
+1 z
+2
+3

(seven values for the seven f orbitals)

(iv) Magnetic quantum number(m) tells about the orientation of an orbital in space relative to other
orbitals. For example, the three dumbbell shaped p orbitals(px, py and pz) are lying along three mutually
perpependicular axes(x, y and z). These p-orbitals are represented by the m values -1, 0 and +1. Each value
will represent one p orbital lying along a particular axis. So from the value of m, we can know along which
direction the orbital is oriented. Similarly for d- and f- orbitals, from the value of l, the orientation of the orbital
can be known.
(v) All the orbitals of a subshell possess same energy. For example, all the three p-orbitals(px, py and pz)
possess equal energy. Similarly all the five d orbitals possess equal energy and all the seven f orbitals possess
equal energy. Orbitals possessing equal energy are called the degenerate orbitals.The three p orbitals are
degenerate, the five d orbitals are degenerate and also seven f orbitals are degenerate.
(vi) Zeeman and Stark effects: In the presence of strong external magnetic or electric field, each line
in the H-spectrum was split into a few finer lines. These are called Zeeman and Stark effects resepctively.
When external magnetic or electric field is applied along a particular direction, the electrons present in
different orbitals interact with the external field to different extents and so posses slightly different energy
values. Thus they no longer remain degenerate. The transition energies for these orbitals become slightly
different from each other and so produce a few finer lines instead of one single line.
SAQ 24:
(i) Give the magnetic quantum numbers for the p- subshell. How many orbitals does the p-subshell
contain?
(ii) How many m values are possible for l=2? What does it mean? Also give the absolute m values for
all these.
(iii) How many orbitals can a s-subshell have? How can you justify through l and m value.
(iv) How can you prove through quantum numbers that a f-subshell has seven orbitals.

4. Spin Quantum Number(s)

(I) Using spectrometers having high resolving power it was observed that each line in the H-spectrum
was split into two finer lines(doublet). This led to the belief that electron besides rotating around the nuclues,
also spins about its own axis(analogous to earth). The spinning of the electron can be either clockwise or
anticlockwise which differ slightly in the energy values. This small difference in transitional energy creates
splitting of a line into two finer lines. This led to the introduction of the 4th quantum number called 'spin
quantum number(s)' which represents the relative spin of electrons in an orbital, whether clockwise or
anticlockwise.
(ii) It takes values +½ (spin up) or -½.(spin down). If +½ will indicate the clockwise spin of the electron
then -½ will indicate the anticlockwise spin of the electron or vice versa. The clockwise and anticlockwise
spins are also reprsented by the symbols ↑ and ↓ respectively. Note that these values(+½ and -½) do not
have any physical significance. These are merely values assigned to the two different spins of an electron.
(iii) Because of electron spin it is associated with spin angular momentum which is represented by
Spin angular momentum = s(s+1) h/2π (where s = spin quantum number = ½ )
Total spin in an atom(St) is given by the
St = ½ × n (where n= number of unpaired electron in an atom)
Since each spinning electron produces a magnetic field and behaves like a bar magnet it is associated with
spin magnetic moment(μs) given by
 μeffective = 4S(S +1) (where S = total spin)

μeffective = n(n+2) BM (where n = number of unpaired electrons)

SAQ 18:
(i) An electron has the following quantum numbers. n=3, l=1, m=-1 and s=+½,
Give the identity of the electron.
(ii) An electron has the following quantum numbers: n=2, l=0, m=0 and s=+½. Designate it.
(iii) Can an electron have the following set of quantum numbers: n=2, l=0, m=+1 and s=-½ ?If not
give reason and indicate which value is not possible?
(iv) Can an electron have the following set of quantum numbers: n=4, l=2, m=-3 and s=+½. Give reason.
(v) Give all possible quantum numbers to an electron present in a 4s orbital.
(vi) Give all possible quantum numbers to an electron present in a 2p orbital.
(vii) Give all possible quantum numbers to an electron present in a 3dyz orbital.
(viii) Give all possible quantum number to an electron present in 5fxyz orbital.

PAULI'S EXCLUSION PRINCIPLE:

From the discussion on quantum numbers, we know now, that a principal shell consists of a fixed number
of subshells and each subshell further consists of a fixed number of orbitals. Each orbital carries electrons.
But the question is how many electrons at the maximum can be accommodated in one orbital and in which
way? This is known from Pauli's Exclusion Principle which states that:
No two electron can have all the four quantum numbers same.
At the most three quantum numbers namely n, l and m can be same for two electrons. But the fourth quantum
number(s) have to be different. In other words the two electrons may be present in the same shell(n), same
subshell(l) and same orbital(m), but they cannot have the same spin. Thus the forth quantum number i.e spin
quantum number(s) have to be different. If one spins clockwise(s=+½), the other spins anticlockwise(s=-½).
Let us take the example of two electrons.
1st electron 2nd electron
n=3 n=3
l= 2 l= 2
m = -2 m = -2
s = +½ s = -½
The two electrons have the same n, l and m values i.e both remain in the 3rd shell(n=3), d-subshell(l=2) and
the same orbital(m=-2), but their spin quantum numbers(s) are different. If one spins clockwise(s=+½), the
other spins anticlockwise(s=-½).
Alternative Definition: An orbital at the most can accommodate two electrons with opposite spins, i.e
if one electron spins clockwise(s=+½), the other electron has to spin anticlockwise (s=-½). If the
upward arrow mark indicates clockwise spin(spin-up) of one electron then the downward arrow mark will
indicate anticlockwise spin(spin-down)for the other electron present in the same orbital.

Explanation: You know that electrons are negatively charged particles. There will be great amount of
repulsion between them. So how can they stay in one single orbital ? They coexist by spinning in opposite
directions. You know that a spinning charge is just like a bar magnet, and the direction of the magnetic field
can be known from the right hand rule. When two electrons in one room spin in opposite directions, their
magnetic fields lie in opposite directions and cancel each other. This results in some attraction between them
which reduces the huge electrostatic repulsion to a large extent. So the two electrons remain together in one
orbital.

SAQ 19:
(i) Explain why after filling one electron in an orbital, second electron does not go to a higher orbital
rather it remains in the same orbital with opposite spin?
(ii) Supposing an orbital has two electrons with opposite(antiparallel) spin. Can the third electron stay
with them in the same orbital? If not, why?

Calculation of electrons in different Shells, Sub-shells and Orbitals:

Let us now calculate total number of electrons that can remain in different subshells and shells on the basis
of quantum numbers and Pauli's exclusion principle.
K shell (1st shell):
n=1, l =0, m=0, s = +½ and -½ ---------> 2 electrons
Thus the 1st shell contains 2 electrons present in the s-orbital.
L shell (2nd shell):
n=2, l= 0 (s-subshell) m= 0 (s-orbital) s=+½ and -½ (two electrons)
So total electrons in s-subshell -----> 2 electrons
= 1 (p-subshell) m= -1, 0, +1(three p-orbitals)
For each orbital s= +½ and -½(two electrons)
Total electrons in p-subshell=3×2 --->6 electrons
________________________________________
Total number of electrons in L shell ------> 8 electrons
Thus the 2nd shell contains 8 electrons out of which 2 are in s-subshell(s-orbital) and 6 in the p-subshell(three
p- orbitals).

M shell(3rd shell):
n=3 l= 0 (s-subshell) m= 0 (s-orbital) s=+½ and -½(two electrons)
So total electrons in s-subshell -----> 2 electrons

= 1 (p-subshell) m= -1, 0, +1(three p-orbitals)

For each orbital s= +½ and -½(two electrons)
Total electrons in p-subshell=3×2 --> 6 electrons
= 2 (d-subshell) m= -2, -1, 0, +1, +2(five d-orbitals)
For each orbital s= +½ and -½(two electrons)
Total electrons in d-subshell=5×2 -->10 electrons
________________________________________
Total number of electrons in M shell ---> 18 electrons
3rd shell contains 18 electrons out of which 2 are in s- subshell, 6 in p-subshell and 10 in d-subshell.

N-Shell (4th shell):

n=4 l= 0 (s-subshell) m= 0 (s-orbital) s=+½ and -½(two electrons)
So total electrons in s-subshell -----> 2 electrons

= 1 (p-subshell) m= -1, 0, +1(three p-orbitals)

For each orbital s= +½ and -½(two electrons)
Total electrons in p-subshell=3×2 ---------> 6 electrons
= 2 (d-subshell) m= -2, -1, 0, +1, +2(five d-orbitals)
For each orbital s= +½ and -½(two electrons)
Total electrons in d-subshell=5×2 ----> 10 electrons
= 3 (f-subshell) m=-3, -2, -1, 0, +1, +2, +3 (seven f-orbitals)
For each orbital s= +½ and -½(two electrons)
Total electrons in f-subshell=7×2 --------> 14 electrons
________________________________________
Total number of electrons in N shell ----> 32 electrons
Thus 4th shell has 32 electrons- 2 in s-, 6 in p-, 10 in d- and 14 in f-subshells..
The total number of electrons in a shell = 2n2
(where n=principal quantum number or the shell number):
1st shell: 2 × 12 = 2 electrons; 2nd shell: 2× 22= 8 electrons
2
3rd shell: 2 × 3 =18 electrons; 4rd shell: 2 × 42 = 32 electrons
The total number of orbitals present in a shell = n2
For example in the 3rd shell the number of orbitals = 32 = 9 (one s + 3 p + 5 d orbitals)
SAQ 20:
(i) Calculate the maximum number of electrons that can be accommodated in the 5th
shell.
(ii) Show by calculations how many electrons can a p-subshell can accommodate.
(iii) How many electrons can a d-subshell accommodate? How can you justify that.
(iv) How many orbitals are present in 5th shell and what are these?
HUND'S RULE
This rule speaks about how shall we distribute and fill electrons in a set of degenerate orbitals. You know
that orbitals having same energy are called degenerate orbitals. The three p-orbitals are degenerate, the five
d orbitals are degenerate and the seven f orbitals are degenerate.
Definition:
Electron pairing occurs only after filling one electron each with parallel (same)spin to a set of
degenerate orbitals.
Let us take another example. Supposing we have three electrons to fill the three degenerate p orbitals. Look
to the following three possibilities.
(i) (ii) (iii)

(wrong) (wrong) (correct)

(i) is wrong because electron pairing starts from the first orbital and one orbital is left vacant without
containing any electron.
(ii) is also wrong even though each orbital is singly occupied, electrons do not have the same spin.
In second and third orbitals the electrons spin clockwise while in the first orbital electron spins anticlockwise.
According to Hund's rule all the unpaired electrons filled in the degenerate orbitals should have the same or
parallel spin, i.e either all clockwise or all anticlockwise. Conventionally we show all clockwise.
(iii) is thus the correct filling diagram.
Explanation of Hund's Rule:
Supposing you with two other friends go to a building which contains three adjacent rooms. Each room has
one plate of your most favourite dish, say ice-cream. How will three of you distribute in these three rooms
of same nature? Will two of you crowd in one room and the other go to the second room or three of you
go to different rooms and remain single in each room and comfortably eat your favourite dish, ice-cream?
Undoubtedly, the second possibility is most favourable. If the fourth friend of yours comes to the same place,
then he will have no other way than to share with one of you. Similarly, when there are three electrons to
fill three p orbitals of same energy, they will spread in the three rooms first with single occupancy and then
if the fourth electron comes, it will pair in one of the singly occupied orbitals. Usually we show it in the first
orbital(left most) of the electron box diagram. Actually all the three electron boxes representing orbitals are
same and pairing can start from any orbital. For convenience, we start from the LHS.
SAQ 21: Give the electron filling diagram for the following electrons. Calculate the number of unpaired
electrons in each case.
(i) d7 (ii) p3 (iii) d4 (iv) f10 (v) p2 (vi) d6
SAQ 22: Explain why the unpaired electrons cannot spin in opposite directions when occupy the
degenerate orbitals? They spin always with parallel spin, why?
AUFBAU PRINCIPLE
A lower energy configuration is more stable than a higher energy system. So When electrons are filled in
different orbitals, first the electron is filled in a lower energy orbital and then in a higher energy orbital. This
is called Aufbau principle. The German word, aufbau means to build up, which means the electrons are
to be added up systematically in orbitals with increasing energy values. We know that shell-wise the increasing
order of energy values is
1(K)<2(L)<3(M)<4(N)<5(O)<......
Subshell-wise the increasing order of energy values is
s<p<d<f
So if we consider both the subshells and shells into account the expected order of the energy levels with
increasing order is
1s< 2s<2p <3s<3p<3d <4s<4p<4d<4f <5s<5p<5d<5f.......... (wrong)
Although this is the expected order of filling the electrons, several factors complicate the situation and change
the order at many places. The complicating factors which creep in as more and more electrons are added
in the different orbitals will not be discussed now. However, a general rule which determines the actual order
of energy levels will be discussed. This is called the (n+l) rule. The aufbau rule is based on this (n+l) rule.
(n+l) Rule:
The orbital having greater value of the sum, (n+l) will have greater energy and if the (n+l) values
are same for two orbitals then the orbital having greater n value has greater energy. n and l are the principal
and azimuthal quantum numbers respectively.
Example: 2s and 2p: For 2s = n+l = 2+0=2 and for 2p= 2+l =3
Since 2p orbital has greater n+l value than 2s, the order of energy is 2s<2p
3d and 4s: For 3d = n+ l = 3+2=5 and for 4s = 4+0=4, 4s<3d
Note that although we expected that 3d should be of lower energy than 4s, in reality it is the opposite.
4d and 5s: For 4d = n+l = 4+2=6 and for 5s = n+l = 5+0=5, so 5s<4d

2p and 3s: For 2p= n+l = 2+1=3 and for 3s=n+l = 3+0=3, In this case the (n+l)
values are same for the two orbitals. According to rule, 3s has greater n value(3) than 2p(2), so 3s possess
more energy than 2p. Conversely 2p has less energy than 3s. 2p<3s
SAQ 23: Indicate the increasing order of energy in each pair by applying the (n+l) rule
(i) 4p, 4d (ii)6s, 4f (iii)5s, 4f (iv)5s, 4p (v)4f, 5d

Using the (n+l) rule the correct order of energy levels is as follows:

1s<2s<2p<3s<3p<4s<3d<4p<5s<4d<5p<6s<4f<5d<6p<7s<5f<6d<7p....

To remember this order in an easy way, there is another very simple and interesting method. You have to
make an arrow diagram as given below. First write the similar orbitals in the same columns. All the s orbitals
will fall in one column, all the p orbitals will fall in the adjacent column followed by all the d orbitals and then
the f orbitals. Then draw parallel and slanting lines passing through the orbitals. Then put downward arrow
marks to each line. Finally join the head of each line(arrow)to the tail of the next line as drawn in this diagram
below.
Filling Arrow Diagram:

We have to follow the arrow to fill the orbitals with increasing energy.
Explanation for (n+l) rule:
The gap between the (n-1)d subshell and ns subshell is small. Since s- orbital has a greater penetration power
it is attracted by the nucleus to a greater extent. Therefore ns subshell assumes slightly lower energy than
(n-1)d subshell.

As electrons are gradually filled in the orbitals several complicating factors creep in. These include
(a)penetration power of the orbitals (b)screening or shielding effect of inner electrons to
the outer electrons(discussed later)(c)electron-electron repulsion present in the orbitals (d)nuclear pull
These effects constantly vary and sometimes nullify each other. The net effect decides the order of energy
among orbitals. Although (n+l) rule is the basis of ordering the orbitals, violation to the rule occurs at some
places and exact reason for the violation cannot be predicted. However the ECs of such elements have been
corroborated by the magnetic moment studies.

ELECTRONIC CONFIGURATION:
Electrons are filled according to aufbau order given above. The maximum capacity of s-, p-, d- and f-
subshells are 2, 6, 10 and 14 resectively.
Example1 Na(11): 1s2, 2s2, 2p6, 3s1
Shell wise Configuration:
If we add all the electrons present in each shell, the configuration will be
Na = 2,8,1
The 1st shell will contain 2 electrons, the 2nd shell 8 electrons(2+6) and the 3rd shell 1 electron. This is the
electronic configuration that students use to write in lower level classes.
Valence Shell:
The last shell in an atom is called the valence shell. In case of sodium that we discussed before, the 3rd shell
is the valence shell. It has only one electron(3s1).
Lone pairs: The electron pairs present in the valence shell are called the lone pairs.
To know the number of unpaired electrons and lone pairs we have to draw the box diagram(filling diagram)
of all the subshells of the valence shell. In this case we have to draw the box for the 3s orbital.

1 So that the number of unpaired electrons is one in sodium.

3s

Example 2: N(7): 1s2, 2s2, 2p3. Shell wise = 2, 5

The 3 electrons in the valence shell are arranged according to Hund's rule.

2s
2
2p 3
The number of lone pairs(LP)= 1 and number of unpaired electrons(UP) = 3.
Example 3: Cl(17): 1s2, 2s2, 2p6, 3s 2, 3p5. Shell wise it will be, 2, 8, 7
The valence shell in this case is the 3rd shell and that contains 7 electrons, out of which two are in s and
remaining 5 are in p-subshells.

3s2 3p5
The number of lone pairs = 3 and number of unpaired electrons =1
Example 4: Ca(20): 1s2, 2s2, 2p6, 3s2, 3p6, 4s2
Shell-wise the configuration is: 2, 8, 8, 2.
In this case the valence shell is the 4th shell.

So we find that there is no unpaired electron. But there is one lone pair.
4s 2

Example 5: Fe(26): 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d6

Shell-wise configuration: 2, 8, 14, 2
In this case, we have to draw both 4s and 3d subshells. Since 3d subshell has 6 electrons and is incomplete,
it must contain unpaired electrons. Note that although the valence shell is the 4th shell, we have to draw the
box diagram of 3d as it contains unpaired electron and practically it is included in the valence shell. This is
because the energy gap between ns and (n-1)d subshell is very small.

UP = 4
4s2 3d 6
SAQ 24: Write the electronic configuration both subshell wise and shell-wise for the following. Also
draw the box diagram of the valence shell and other incomplete subshell, if any, and find the number of
unpaired electrons in each case.The atomic numbers are given within brackets.
He(2), Be(4), B(5), C(6), O(8), F(9), Ne(10), Mg(12), Al(13), Si(14), P(15), S(16), Ar(18), K(19), Sc(21),
Ti(22), V(23), Mn(25), Co(27), Ni(28), Zn(30), Br(35), I(53), Sn(50), Hg(80)

Stability of Half-filled and Full-filled Subshell configuration:

(Configuration of Cr and Cu)
We know from (n+l) rule that 4s<3d, but their energy difference is very small. Exchange of electron from
4s-subshell to 3d subshell sometimes occurs particularly when there is extra stability achieved due to full-filled
and half filled subshell configuration. Look to the following case to get a better understanding. The expected
electronic configuration of Cr(24) is given below.
Cr(24): 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d4 (wrong)

4s2 3d 4
In this configuration there are four unpaired electrons in Cr. But actually Cr contains six unpaired electrons
which has been revealed from experiment. How can we account for this?
Actually one electron slips from the 4s subshell to the vacant 3d subshell, then both the subshells become
half filled. The maximum capacity of s-subshell is 2 and that of d-subshell is 10. So 1 and 5 electrons make
them half-filled respectively. Since half-filled or full-filled subshell configuration are more stable, such a
shifting of electron occurs from 4s to 3d. So the correct configuration is:
Cr(24): 1s2, 2s2, 2p6, 3s2, 3p6, 4s1, 3d5 (correct)

4s2 3d5
In this configuration of Cr, we find a total of six unpaired electrons.
Cu(29): 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d9 (wrong)
In this case too, one electron from 4s subshell goes to the 3d subshell to make it full-filled(3d10) and itself
becomes half filled. Since this is more stable configuration, the correct configuration is
Cu(29):1s2, 2s2, 2p6, 3s2, 3p6, 4s1, 3d10 (correct)

4s2 3d10
In this configuration of Cu, the 3d subshell is complete(10) and 4s subshell contains one unpaired electron(half
filled).
Explanation:
When (n-1)d-subshell becomes half filled or full filled, it acquires a symmetrical structure for which
its stabilty increases. This is accompanied by the loss of some energy called symmetry energy. This energy
provides for the unpairing of one ns electron and its promotion to (n-1)d subshell. This occurs when the d-
subshell is one electron short of the half filled or full filled configuration. Note that the energy gap between
(n-1)d and ns subshells is small and symmetry energy evolved is numerically greater than the sum of the
energy needed for the unpairing and promotion of one ns electron to the vacant (n-1)d orbital.
This is also explained by Exchange energy concept. If three are four unpaired elections in the d-subshell,
then the total number of exhanges is 6 (1 to 2,3 and 4. Then 2 to 3 and 4 and finally 3 to 4). If there are
5 unpaired electrons, the total number of exhanges is 10 ( 1 to 2,3,4, 5, then 2 to 3, 4 5 and 3 to 4, 5 and
finally 4 to 5). Greater the number of exchanges, greater is the exchange energy evolved and hence greater
is the stability of configuration.
Caution: Note that such a transition does not take place between ns to np subshell as the energy gap between
them is large.
Electronic Configuration of Ions:
Example: Na+:( number of electrons = 11-1 = 10 )
Na (10): 1s2, 2s2, 2p6: (2, 8). Thus we find that 1st and 2nd shell are complete and there is no
+

unpaired electrons = Ne configuration (there is no unpaired electron)

Cl-: (number of electrons = 17+1=18) = same as Ar configuration
Cl-(18): 1s2, 2s2, 2p6, 3s2, 3p6 (2, 8, 8). (there is no unpaired electron)

Electronic configuration of transition metal ions:

Electron is first lost from the ns subshell and then from the (n-1)d subshell. This is because while filling
electrons the order of energy is ns < (n-1)d. But after the electrons are filled up the order gets reversed
i.e ns > (n-1)d. That is why ns electrons are lost first. This is explained through screening effect.
Screening effect: The electrons of the inner shells act like a screen or mechanical barrier to reduce the force
of attraction between the nucleus and the electrons of the outermost shell. The screening effect produced
by different subshells are different. The order of screening effect is as follows
s > p > d > f (same as the order of penetration power disscussed before)
When electrons are filled in the (n-1)d orbital, the screening effect of (n-1)d orbitals onto the ns(outer shell)
orbitals comes into force. Before that there is no screening effect. This screening of d- electrons reduces
the nuclear pull onto the ns electron to a small extent. Therefore the energy of ns subshell exceeds that of
(n-1)d subshell.
EC of Fe2+ : Fe(26) = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d6

Fe2+ = 1s2, 2s2, 2p6, 3s2, 3p6, 4s0, 3d6 (4 unpaired electrons)
4s2 3d6
Fe3+ = 1s2, 2s2, 2p6, 3s2, 3p6, 4s0, 3d5 4s2 (5 unpaired electrons)
3d5
SAQ 25: Write the electronic configurations of the following. Find the number of unpaired electrons.
(i)Co3+ (ii)S2- (iii)Cr3+ (iv)Cu+ (v)Zn2+ (vi)Mn4+
Paramagnetic Species: The species which contain one or more unpaired electrons are called paramagnetic
species. Such a species is weakly attracted by an external magnet.The magnetic dipole moment(μ) of such
a species is given by
μ = n(n+2) B.M (Bohr Magneton) 1 BM = 9.27 × 10-24 Joule/Tesla
Examples: Na, Cu, Cr etc.
Ferromagnetic species: Those which are strongly attracted by a magnet(Fe, Co, Ni, Gd, Dy) and can be
permanently magnetised are called ferromagnetic. Paramagnetism is a weaker form of ferromagnetism and
paramagnetic species cannot be permanently magnetised. Ferromagnetic species become paramagnetic above
a critical temperature(Curie temperature). Fe becomes paramagnetic above 1043K.
Diamagnetic species: Those which do not have any unpaired electrons are called diamagnetic species. Such
species is weakly repelled by an external magnet. The net magnetic dipole moment of such species is zero.
SAQ 26:
(a)Calculate the magnetic dipole moment of the following ions. (i) Fe3+ (ii)Cu+ (iii)K (iv)Cr
(b) The magnetic dipole moment of Co2+ was experimentally determined to be 3.79 BM. Predict the number
of unpaired electrons present in it.
NOTE: The EC of many transition and inner transition metals have been corrected from the experimental
value of the magnetic dipole moment. Because the energy gap between ns and (n-1)d subshell is small, and
also the gap between (n-1)d and (n-1)f subshell is small, transition of ns electron to (n-1)d orbitals occurs
at many places in the transition metals. and beween (n-1)d and (n-2)f orbitals occur in some inner transion
elements.
Isotopes, Isobars and Isotones
We have studied in details about isotopes in the chapter, Atomic Mass.
Isobars are different elements which have the same mass number. For example: 18Ar40, 19K40 and 20Ca40
have same mass numbers(40), but they have different atomic numbers. They differ both in the number of
their protons and neutrons.Another pair of isobars is 22Ti50 and 24Cr50.
Isotones are different elements but have same number of neutrons in their nuclei.19K39 and 20Ca40 have
same number of neutrons(20) and are isotones.
Isodiaphers:
In nuclear physics, isodiaphers refers to nuclides which have different atomic numbers and mass numbers
but the same neutron excess, which is the difference between numbers of neutrons and protons in the
nucleus. For example, for both 90Th234 and 92U238 the difference between the neutron number (N) and proton
number (Z) is N - Z = 54.
One large family of isodiaphers has zero neutron excess, N = Z. It contains many primordial isotopes of
elements up to calcium. It includes ubiquitous 12
6
C12, 8O16, and 7N14.
The daughter nuclide of an alpha decay is an isodiapher of the original nucleus. Similarly, beta decays (and
other weak-force-involving decays) produce isobars.
SAQ 27: Indicate which pair of elements are isotopes, isobars and isotones.
(i)6C14, 7N14 (ii)6C12, 6C13 (iii) 1H1, 1D2 (iv)5B11, 6C12
60 60 18 19
(v)27Co , 28Ni (vi)8O , 9F

Shapes of orbitals and signs of lobes:

s-orbital: Spherically symmetrical. The sign of the orbital is +.
Sign of lobes: The lobes of orbitals are given signs + or -. These are nothing to do with electrical
charge. This is related to the symmetry of the lobes in an orbital obtained from the signs of the angular
part of the wave functions of the Schrodinger's wave equation. Their application will be discussed in
the chapter chemical bond.
s-orbital has no angular node. Node is surface in which the probability of finding the electron is zero.
p-orbitals: There are three p orbitals namely px, py and pz. Each orbital has two lobes lying on the opposite
side of the nucleus on x, y and z axes respectively. This is called dumbbell shaped. The oppsite lobes carry
opposite signs. If one lobe is + , then the other lobe of the orbital is -. Each has one angular(planar) node
passing in between the lobes. yz, zx and xy planes are the angular nodes for px, py and pz orbitals respectively.
d-orbitals:
The shape of a d-orbital is often called a double dumb-bell shaped. Actuall 4 out of the 5 d-orbitals contain
four lobes each. But d z 2 orbital has three lobes out of which two lie along z-axis and the other is a doughnut
shaped ring(torus) around the centre in the xy plane. In case of dxy, dyz and dzx orbitals the lobes lie in
between the axes specified in their designations and in case of d x 2  y 2 , the lobes lie along the x and y axes.

(note that

In a d-orbital the opposite lobes carry same sign. If one pair of lobes get + the other pair gets -. In the dz2
orbital, if the two lobes along z-axis gets + sign the ring along xy plane gets - sign. Note that in the 2D
diagrams given above, the axes are constantly changed for a better clarity of pictures. Acutally the set of
axes though arbitrary are fixed which are shown in the 1st set of 3D pictures.
Excepting dz2 orbital each of the other four has two angular(planar) nodes which pass in between the lobes.
For dxy the nodal planes are yz and zx planes, for dyz the nodal planes are xy and zx planes while for dzx
the nodal planes are xy and yz planes. For dx2-y2 orbital the nodal planes pass in between the x and y axes
perpendicular to the xy plane which intersect at the z-axis. dz2 orbital has two angular(conical) nodes- each
conical surface starts from the nucleus and surrounding each lobe on either side of the xy plane.
f-orbitals:
There are two sets of f-orbitals- (i)general set and (ii)cubic set. The general set of f-orbitals are given
below.The two sets have three f orbitals in common ( f xyz , f z x 2  y 2  and f z 3 ). The designations of the seven

f-orbitals in the general set are already given before. The 4 uncommon f orbitals in the cubic set are f x 3 ,
f y 3 , f x  y 2  z 2  ) and f y x 2  z 2  . The following descriptions are given for the general set.

f x x 2 3 y 2  (m = ±3): It contains 6 lobes pointing to the cornors of a regular hexagon in the xy plane with
one pair of lobes along the x-axis. It has 3 angular(planar) nodes passing in between the lobes which intersect
at the z-axis with an angle of 600 between them. In case of a f orbital, the opposite lobes get the opposite
signs like a p-orbital.

f y 3 x 2  y 2  (m = ± 3): It similar to the above except that one pair of lobes lie along y-axis. One orbital is
converted to the other by 900 rotation.
f xyz (m = ± 2):

It contains eight lobes pointing to the corners of a cube with four lobes above and four below the xy plane.
It has 3 angular(planar) nodes i.e xy, yz and zx planes.
f z x 2  y 2  (m= ± 2) : It is similar to fxyz orbital. If the fxyz orbital is rotated by 450 about z-axis it will be

converted to f z x 2  y 2  orbital. Lobes in this orbital lie on the zx and yz planes. It contains 3 angular(planar)
nodes out of which 2 lie in between the lobes perpendicular to xy plane and the third node is the xy plane
itself.
f xz 2 (m = m= ±1)

It contains six lobes pointing to the corners of a regular hexagon in the xz plane with one pair of lobes lying
along x-axis. The lobes lying along x-axis are bean shaped. It has 3 angular(planar) nodes which pass in
between the lobes .
f yz 2 (m= ±1):
It contains six lobes pointing to the corners of a regular hexagon in the yz plane with one pair of lobes lying
along y-axis. The lobes lying along y-axis are bean shaped. It has 3 angular(planar) nodes which pass in
between the lobes . f xz 2 and f yz 2 are interconvertible by a rotation of 900 about a vertical axis(z axis).
f z 3 (m =0)

Two lobes lie along z-axis with two bowl shaped rings above and below the xy plane. It has 3 angular nodes
out of which one is planar(xy plane) and the other two are conical nodes through the nucleus and between
the rings and lobes on either side of the xy plane.
( In the cubic set, f xz 2 , f yz 2 , f x x 2 3 y 2  , f y 3 x 2  y 2  are replaced by f x 3 , f y 3 , f x  y 2  z 2  ) and f y x 2  z 2  orbitals.

f x 3 and f y 3 are similar in shapes as f z 3 while f x  y 2  z 2  ) and f y x 2  z 2  are similar in shapes as fz(x2-y2)

NODES
The Schrodinger's wave equation for the electron is given below. This is a differential equation involving x,
y and z coordinates(3D). The solution of the equation is beyond the present scope.
 2  2  2 8 2 m
   ( E  V )  0
x 2 y 2 z 2 h
Where Ψ is the wavefunction(eigenfunction) related to the amplitude of the electron wave. E is the total
energy of electron(eigenvalues) and V is the potential energy of electron. Ψ does not have any physical
significance. However Ψ2 has a great physical significance. Ψ2 is related to the probability of finding the
electron at a point or per unit volume element possessing a particular energy value at a particular radial
distance with resepct to the nucleus. This is called Electron Probability Density(Electron Density) The
probability(D) of finding an electron at a distance 'r' from the nucleus within a concentric small volume
element is given by the radial distribution function(D)
D = 4πr2 × R2 (where R = radial component of Ψ)

NODE: It is the surface in space surrounding the nucleus on which the probability of finding the electron
at any point on the surface is zero. Nucleus and infinite distance are not considered as nodes although the
probability of finding the electron in these points is zero(radial probability). Orbitals may or may not have
nodes. There are two types of nodes: (a)radial node(spherical node) (b)angular node(planar/
conical nodes)
Radial Nodes:
Radial node is a spherical surface with a fixed radius from the nucleus and radial component of the wave
function(D) is zero at any point on this surface. The angular node is usually a planar surface but sometimes
it is a conical surface(dz2 and fz3). Any s-orbital is only radius dependent for finding the electron's probability
as it is spherically symmetrical. In other words it is not angle dependent. and hence has only radial node and
not angular nodes. However p, d, f, g orbitals are both radius and angle dependent for finding this probability.
Hence they have both radial as well as angular nodes.
D - radial distance(r) graphs for different orbitals are given below.

1s: Maximum point of the graph: most probable radial distance ≡ Bohr's radius of 1st shell a0 = 0.529Å.It
has no radial node.
2s: Two maxima: princial maximum = 5a0 (most probable radial distance for 2s orbital) , subsidiary maximum
= a0 . In between the two maxima, the curve touches x- axis(D=0) at r = 2a0 = radius of the spherical node.
Hence 2s orbital has one radial node
2p: most probable radial distance = 4a0 . It has no radial node
3s: Two subsidiary maxima at a0 and 4a0 , principal maximum at 14a0 (most probable radial distance for 3s
orbital), Nodes at 2a0 and 8a0.
3p: Subsidiary maximum(3.2a0) and principal maximum(13a0). Hence it has one radial node(5.2a0)
3d: Most probable radial distance = 9a0 and it has no radial node.
Conclusion: Number of radial nodes = n - l - 1
1s = no node, 2s = 1 node; 3s = 2 nodes and so on
2p = no node; 3p = 1 node; 4p = 2 nodes and so on
3d = no node; 4d = 1 node; 5d = 2 nodes and so on
4f = no node; 5f = 1 node; 6f = 2 nodes and so on.

ANGULAR NODES:

s-orbital = no node; Any p orbital = 1 angular(planar) node passing in between the lobes(eg for pz orbital
the xy plane is the angular node, for px = yz plane and for py = zx plane)
Any d orbital: 2 angular(planar) nodes passing in between the 4 lobes except the two angular nodes of dz2
are conical in nature.
Any f-orbital: 3 angular(planar) nodes passing in between 6/8 lobes except for fz3 orbital the two are conical
and the third is planar.
SAQ: Designate the orbital and find out the radial and angluar nodes in each case.

Solution: (A) 4d orbital(other than 4dz2) : 4 lobes while each lobe is split at the radial node:
 No. of Radial nodes: 1; No of anglular(planar nodes) =2
(B) Any 4f orbital :(6 lobes) No of radial nodes = 0; No of angular(planar node) = 3
(C) Any 3d orbital(other than 3dz2) 4 lobes. No of radial nodes = 0; No. of angular nodes = 2
(D) 4fz3 : the two bowl shaped lobes are looking like four lobes. No ob radial nodes = 0, No of angular
nodes = 3

MOSELEY'S EXPERIMENT ON DISCOVERY OF ATOMIC NUMBER

First Moseley determined the graph for the frequency(√ν) of x-rays emitted vs. atomic masses of
elements and found a nearly linear relationship(not strictly linear). The linear relationship broke out at few
places like (K, Ar), (I,Te), (Co, Ni) etc. When he determined the graph of √ν vs. serial number of the element
in the PT he found perfect linear graph. He termed the serial number of element as atomic number i.e the
number of protons present in the nucleus.

√ν = a(Z-b)
(where Z= serial number = atomic number of element, a and b are constants for an element.
(Note that Kα series of lines of metals are those representing transition of electron from n=2 to n=1; Lα series
for transition from n =3, to n =2 and Mα series from n =4 to n =3.
SAQ: If the straight line at an angle of 450 in the plot of √ν vs Z graph gives an intercept of 1 in the y axis(-
ve). Predict the frequency of x-rays produced when cathode rays strike on tin metal(Z=50).
PHOTOELECTRIC EFFECT:
Photoelectric effect is the process of the ejection(called photoelectron) of electron from a suitable
(called a photoemissive/photoconductive material) metal surface when uv/visible light is incident upon it. The
photoelectric effect was first properly described by Albert Einstein. The classical wave theory of light failed
to describe most of the observations of the photoelectric effect. There is a threshold frequency for the
incident waves below which electrons are not ejected from the surface. This indicates that no matter how
intense the light waves are, electrons would not be ejected unless it has the required frequency. The time
delay between the incidence of light and the ejection of electrons is about a thousandth of the value calculated
from the wave theory. When light exceeding the threshold frequency is incident, the number of emitted
electrons depends on the intensity of the light. The maximum kinetic energy of the ejected electrons depends
on the frequency of the incident light. The intensity of incident light had no effect on maximum KE of
photoelectrons, although the number of photoelectrons ejected increases due to that. This led to the conclusion
of the photon theory of light. This means that the light behaves as stream of discrete particles when
interacting with matter. The light comes as small packets of energy called photons. The energy of the photon
only depends on the frequency of the photon(not intensity). There are a few other terms defined in the
photoelectric effect. The work function of the metal is the energy corresponding to the threshold frequency.

When uv/visible light fall on strong electropositve metal(low IE) with another metal plate(collector) located
in front of it, both housed inside an evacuated tube, electrons are ejected out from the metal surface and move
towards to collector plate, provided the energy of incident light photon is greater than the workfunciton of
themetal.. This small current can be detected by microammeter. These are called photoelectrons and the
phenomenon is called photoelectric effect(Einstein). In the absence of the uv/visible radiation, there is no
conduction of electricity.

1 1
h    mv 2 h  h 0  mv 2  KE  h  
2 2

Where hν is the energy of the incident light photon, φ = threshold energy or work function needed to detach
electron from the surface of the metal; 1/2 mv2 = kinetic energy of photoelectron, ν0 = threshold frequency
A graph of KE vs. ν, gives ν0 when KE=0 on the x-axis. The intercept on the –ve y-axis gives the threshold
energy or work function(φ) directly. Interestinlgy slope of the straight line gives the famour 'h' value.
Alkali metals (Na, K, Rb etc) are most suitable photoelectric material as their ionisation energy is small.

Determination of maximum KE of photoelectrons(STOPPING POTENTIAL). The source of

emf(battery) shown in the figure was used only to determine stopping potential(not to produce photocurrent).
When the photoelectric current is in progress, PD is applied on the opposite direction i.e +ve terminal is
connected to the photoemissive metal(under irradiation) and –ve terminal is connected to the other metal
plate. Slowly the PD is increased, more and more photoecctrons are trapped back and stop coming out of
the surface and the magnitude of current decreases. The PD at which current becomes zero is called the
stopping potential. At this potential the electrons with maximum KE stop coming from the surface.From this
stopping potential the maximum KE of photoelectrons can be determined.
1 2
mv  e V S (wehre e = charge of 'e', VS = stopping pd)
2
Explanation: Photoelectrons are ejected without application of any PD in the circuit(as shown in the first
figure). If PD is applied such that photoemissive metal is –ve and collector plate is +ve, the current increases
with increase in PD upto certain extent and thereafter current becomes constant with further increase in PD.
This is due attainment of highest velocity nearer to 'c' by the photoelectrons. Note that more intense radiation
has greater current at each PD than less intense radiation for the same wavalenght. This is shown in the
second figure and last figure(+ve x-axis). When the PD applied in the opposite direction(last group of figures)
going to the –ve x-axis, the current decreases with decrease in the number of electrons produced as well
as reducing the velocity of those ejected out. But at certain –ve PD, the current becomes zero, which means
no photoelectron comes out. This is PD(–ve PD, from origin to zero current) is called the Stopping potential.
Note that for both more intense and less intense radiations, the Stopping potential is same, which proves that
the maximum KE does not depend on the intensity of radition(instead on the frequency of radiation).
SAQ: Calcualte the kinetic energy of the electron emitted when light of frequency 3 X 1015 Hz is alowed
to strike on a metal surface which has a threshold frequency of 1015 Hz ( 1.3 X 10-18 J)
SAQ: Calculate the velocity of photoelectrons when uv light having wavelength 300Å is irradiated on silver
metal surface, if the minimum energy required to covercome the attractive force between the valence
electron and the surface is 6 X 10-19 J.
N.B: The photoelectric effect principle is applicable to a single atom existing in gaseous state also.
For example, you supplied photons having 33.6 eV to H atoms which are in their ground state. 13.6
eV out of it will be used to knock out the electron i.e to bring about ionisation and the remaining 20
eV will impart KE to the ejected electron.
COMPTON EFFECT:
When a monochromatic x-rays beam is allowed to strike on a target substance, the x-rays photon hits on
a loosely bound electron of the element. . The x-ray photon is scattered at an angle θ with respect to its
original direction. The energy of scattered x-rays is reduced because a part of incident photon is taken up
by the recoiled electron.
h
  s  i  (1  cos  ) (where λ =wavelength of scattered photon, λ = wavelength of the
m0 c s i

incident photon, m0 = rest mass of scattering substance(electron), θ = angle of scattering

Δλ = compton shift
When θ = 900, scattered photon has maximum wavelength.Scattered angle is measured in a x-rays spectrometer.
NB: When the energy of the photon is smaller than 1MeV i.e UV and Visible type then scattering effect
is not observed. Instead photoelectric effect is observed.
The particle nature of photon was proved by compton effect.
SAQ: A monochromatic x-ray having wavelength of 0.558Å is scattered through an angle of 460, what is
the wavelength of scattered photon?
SAQ: Designate the oribitals and give the number of radial and angular nodes for each.
 NUMERICAL PROBLEMS
(LEVEL-1)

1. Calculate the frequency of the D,line of sodium (58900A0) (5.09 × 1014sec-1)

2. Find the wavelength in Angstrom for a radiowave having freequency 12*10-5 sec-1 (2.5*104cm)
3. When Cu plate was bombarded with electron beam, X-rays having wavelength 0.15nm was
produced.Calculate the energy of x-ray photon. Also calculate its wave nmuber.(1.32 ×10-8erg,6.67 ×107cm-
1
)
4. Calculate the wavelength in Å for a radiation having wave number 1200cm-1.To which region of the
electromagnetic radiation does it belong (8.33 ×104 A0,IR)
5. The frequency of a radiation is 10 ×109Hz.Find the wavelength & energy of radiation.To which region
of electromagnetic (em)radiation does it belong.(3 ×108 Å, microwave)
6. The energy required to dissociate Cl2 molecules to cl atoms is 239kJ per moles of Cl2. Calculate the
exact wavelength of radiation required to bring about this dissociation. To which region of em spectrum does it
belong? (5010A0 visible)
7. Calculate the radius of 1st Bohr’s orbit of H-atom and consider it as the radius of the H-atom. Calculate
radius of the nucleus of H-atom by using the formula. r = (1.3 ×10-13)A1/3cm (where A=mass no)
From the above results calculate the fraction of the total volume of H-atom that is occupied by the nucleus.
(0.529Å , 1.484 ×10-14)
8. Calculate
a.the radius of the orbit b.velocity of the electron
c.the number of revolutions per sec. of an electron in the 2nd orbit of He+ ion.
(1.058A0,2.18×108,3.31×1015)
9. Calculate the wavelength of the radiation required for the transition of Li2+ Li3+. (101.3A0)
10. Calculate the frequency of light ray emitted when an electron drops from a higher to lower energy level
of an atom. The difference in energy between the two levels is 35.0 ×10-13erg.(h = 6.627 ×10-27erg.sec)
(5.28*1014sec-1)
11. Calculate the wavelength of radiation to be observed for the promotion of electron from the ground
state to the 3rd Bohr orbit of He+ion.(256.4A0)
12. Calculate the frequency of radiation emitted for an electron transition from the sixth to second orbit of
the hydorgen atom. In what region of electromagnetic spectrum does this occur? (4103.06A0,visible)
13. Calculate the radii of the first two Bohr orbit of Li2+. Calculate the difference in total energy between
their orbits.(0.176A0,0.705A0,1.47 ×10-17J).
14. The wave number of the first line of the Balmer series of hydrogen spectrum is 15200cm-1.What is the
wave number of the first line for the electron transition from n=3 to n=2 in Be3+ spectrum. (243200cm-1).
15. Calculate the velocity of electron in fallownig & compare between the two.
a. 2nd Bohr’s orbit of H-atom
b. 1st Bohr’s orbit of He+.(4.36 ×108cm/sec)
16. Predict one electronic transition (n2 n1) in He+ which would result in the emission of visible light?
Explain with calculation(4 3)
17. What transition in the He+ spectrum should have the same wavelength as the first line of the Lyman
series of H-spectrum.What is the 2nd Ionisation energy of He.(4 2)
18. One of the lines of the Balmer series of H spectrum appears at 3970A0.Predict the higher & lower
states of electronic transition for this line. (7 2)
19. Calculate the wavelength of the last lime of the Lyman series.(911.9 A0)
20. Calculate the wavelength (in Å),freequency (sec-1) and wave number (cm-1)of the spectral line for the
transition of electron from n2=4 to n1=2 in Li2+ ion.(540.3 Å, 5.55×1015sec-1,1.85 ×105cm-1)
21. Calculate the energy emitted by the electron for giving the spectral line involving highest energy transition
in the uv region of H-spectrum? Explain your answer in electron volt (ev) (13.6ev)
22. A 1g of bullet is shot from a gun with velocity 500cm/sec.What is its deBroglie wavelength ? (1.325×
10-21Å)
23. Calculate the wavelength in Å associated with a neutron beam moving at a velocity of 5×106cm/sec.
(0.0798Å)
24. The deBroglie’s wavelength for an electron beam is 5A0.Calculate the velocity of electron.(1.456×108cm/
sec)
25. Calculate the wavelength of the electron wave
a. in the 2nd Bohr’s orbit of H-atom.
b.1st Bohr’s orbit of He+ (6.644Å, 1.66Å)
26.Calculate the deBroglie wavelength of an moving electron having energy 150 ev.(1Å)
27.Calculate the wavelength associated with an electron accelerated from rest by a potential difference of
5000v.(0.173Å)

28. An electron has a speed of 3×106cm/sec. Which is accurate upto 99.999%.Calculate the uncertainty
in locating its position in Angstorm. (0.0193cm)
29. If a 2g body travelling along x-axis at 500cm/sec is accurate within 0.5cm/sec. Calculate the uncertainty
in its position.Compare this uncertainty in position with that of an electron moving at the same speed with same
degree of in accuracy. Comment on the results. (2.63 ×10-28cm, 0.58 cm).
30.Calculate the velocity of electron in 1st Bohr’s orbit of H atom using Bohr’s theory. Calculate the uncertainty
in measuring its velocity.it can be located within 0.05A0.Comment on the results.

Level-II

1. A H-like atom(atomic no.Z) is in a higher excited state of quantum number(x).This excited atom can
make a transition to the first excited state by successively emitting two photons of energies 10.2ev and 17ev
respectively. Alternatively,the atom from the same excited state. can make a transition to the second excited
state by successively emitting two photons of energy 4.25evand 5.95ev respectively. Determine the values of
‘x’ and ‘z’.Ionisation energy of hydorgen atom=13.6ev.(x-=6,z=3)
2. A gas of identical H-like atom has some atoms, in the lowest(ground) energy level ‘A’ and some atoms
in a particular upper (excited)energy level’B’and there are no atoms in any other level. The atoms of the gas
make transition to a higher energy level by absorbing monochromatic light of photon energy 2.7eV.Subsequently,
the atoms emit radiation of only six different photons. Some of the emitted photons have energy 2.7eV some
have more & some have less than 2.7ev.
i.Find the Principal quantum number of initially excited level‘B’.
ii.find the ionisation energy for the gas atoms.
iii.Find the max. and min.energies of the emitted photons. [(i) 2 (ii).14.4 eV (iii).13.5 and 0.7 eV]
HINTS: The higher level must be 4 so that there will be 6 transions. On trial and error basis, the transition
energy between 2 to 4 is 2.5 eV in H atom and this is much greater in other species. So the higher state
originally the electron was the 2nd state(B). The ground state species have not undergone transitions(see for
yourself the difference between 1st and 2nd level). It is the B state species have excited to 4th state. The
species is not exactly H1 atom. It is H2(deuterium). Using the 2.7 eV data between 2 and 4 transition , find out
the value of k (14.4 eV) i.e the ionisation energy of deuetrium which is slightly more than H. This suggests the
the nuclear pull inn deuterium is more than hydrogen. The presence of a neutron also is responsible to increase
the nuclear pull.
3. An electron in H atom in its ground state absorbs 1.5 times as much energy as the minmum energy
required for it to escape from the atom. what is the wavelength of the emitted electron?
4. According to Bohr’s theory the electronic energy of H-atom in the ‘n’th Bohr’s orbit is given by En=-
21.7*10-19/n2 x z2 J. Calculate the longest wavelength and the corresponding freequency of light that will be
needed to remove an electron from the third orbit of the He+ ion.(4.85 ×106m-1, 2061.8Å)
5. The IE1 of H is 2.18 ×10-18J. It is exposed to electromagnetic radiation of 1028A0. Which gives out
induced radiations. Find the wavelength of these induced radiations.(6564.7A0, 1028Å)
ELITE-3
6. Find out the number of waves made by an electron is one complete revolution in its 3rd Bohr’s orbit of
H-atom.(3)
7. Iodine molecule dissociates into atoms after absorbing light of 4500A0.If one quantum of radiation is
absorbed by each molecule, calculate the Kinetic energy of iodine atoms.(Bond energy of I2=240KJ mol-
1
)(2.17*10-20J)
8. Estimate the difference in energy between 1st and 2nd Bohr orbit for a H atom. At what minimum
atomic number, a transition from n=2 to n=1 energy level would result in the emission of x-ray with λ =3.0*10-
8
m. Which hydrogen like species does their atomic number correspond to ? (2, He+)
9. An electron beam can undergo diffraction by crystals. Through what potential should a beam of electrons
be accelerated. So that its wavelength becomes equal to 1.54 Å .(62.74v)
10. A compound of vanadium has a magnetic moment1.73BM.Work out the electronic configuration of
vanadium in this compound.(V+4)
11. In a photoelectric effect experiment, irradiation of a metal with light frequency of 2×1016Hz yielded
electron with kinetic energy of 7.5×10-18J.Calculate the threshold frequency of the metal.
(8.67×1017Hz)
12. Calculate the velocity of the phutoelectrom emitted when light of frequency 3×1015Hz is irradiated on
a metal surface having threshold frequency 1015Hz.(1.7×108cm/sec)
13. The photo electron is ejected from certain metal with a light photon having minimum freequency 6.54×1014
sec-1. If light photon having wavelength of 2000A0 is used to irradiate the metal what is the kinetic energy of the
photo electron. (5.6×10-12erg)
14. The photoelectric work function for Mg is 5.9×10-19J. Calculate the wavelength of light required just to
eject photo electrons.(3369.6A0).
15. Helium can be excited to 1s1 2p1 configuration by supplying 33.12×10-19J of energy. The lowest excited
singlet state 1s1 2s1 lies 5000 cm-1 below 1s1 2p1 state. What should be the average He-X bond energy so that
HeX2 could form non-endothermically? Assume the compound would be formed from lowest excited singlet
state of He+. Heat of atomization of X=200kJ mol-1. (1167.5kJmol-1)
HINT : wavenumber from GS to 1s12p1 = 16661463.08 m-1, wave number GS to 1s1 2s1 = 16661463 -
500000 = 16161463.08
m-1,
Energy required per atom = 3.212 × 10-18 J, per mole = 1934678.737 = 1934.678 kJ/mole

2x >= 1934.678 + 2 ×200, x >= 1167.339 kJ/mole

16. Photoelectrons are liberated by uv light of wavelength 3000A0 from a metallic surface for which the
photoelectric threshold is 4000Å. Calculate the de Broglie wavelength of electrons emitted.(1.2×10-7ion)
17. A single electron orbits around a stationery nucleus of charge +Ze,whereZ is a constant and ‘e’ is the
magnitude of electronic charge. It requires 47.2 ev to excite the electron from second Bohr orbit to the 3rd
Bohr orbit. Find:
a. The value of Z
b. the energy required to excite the electron from n = 3 to n = 4.
c. the wavelength of radiation required to remove electron from 2nd Bohr’s orbit to infinity.
d. the kinetic energy, potential energy and angular momentum of the electron in first orbit.(z =5, 16.53ev,
 RESPONSE TO SAQs
(Atomic Structure)
SAQ 1:
(i) Nearly 1840 times because a neutron has almost same mass as a proton.
(ii) - 3 X 1.602 X 10-19 coul. (iii) 2 X 1.602 X 10-19 coul.
(iv) Ten (v) 6.023 X 1023 X 1.602 X 10-19= 96,488 coul. This
is called one faraday(1F ≈ 96,500coul) of charge.
SAQ 2:
(i) The alpha particles emitted out of the radioactive element, polonium are dangerous to environment
and human health. Thick lead sheet is a good absorber of alpha particles. It does not allow the alpha particles
to pass through it. Therefore the radioactive metal, polonium is kept inside a lead box and a thin beam of
alpha rays is allowed to pass through a fine hole.
(ii) It is because alpha particle is much lighter than the nucleus of gold atom. Therefore the impact of
the alpha particle onto the massive gold nucleus is not able to dislocate and dislodge the nucleus from its
original position.
(iii) Gold is a very malleable metal. Malleable means it can be hammered to form very very thin sheet
to extent of 0.0004cm thickness. Imagine how thin such a foil would be!!! Other metals do not have such
malleability and for that reason gold was preferred.
SAQ 3: 1 cm = 108 Å, So 0.001cm = 0.001X 108 Å = 105 Å
Again 1 cm = 107nm, So 0.001cm = 0.001 X 107 = 104 nm
SAQ 4: 1 Å = 10-8cm, So 1000 Å = 1000 X 10-8cm = 10-5 cm.
Again 1 Å = 10-10m, So 1000 Å = 1000 X 10-10= 10-7m.
SAQ 5: (i)UV rays (ii)x-rays (iii)IR rays (iv)Gamma
rays
(v)x-rays (vi)Microwave (vii)Cosmic rays (viii)Visible
rays (ix)Radiowaves.
SAQ 6:
(i) 3 X 1010cm/sec. It is same as the velocity of infrared rays and in fact any other
electromagnetic wave.
(ii) ν = (3 X 1010)/(500 X 10-7)=6 X 1014 sec-1;
Wave number = 1/(500 X 10-7)=2X 104 cm-1.
This wave belongs to visible radiations( 500nm=5000 Å)
(iii) cosmic rays < x-rays < uv rays < microwaves < radiowaves.
(iv) cosmic > gamma > x-rays > uv rays > visible > IR > microwave > radiowaves
(v) Wave number is directly proportional to frequency.
microwaves < visible rays < ultraviolet rays < gamma rays
(vi) x-rays: picture of bones; gamma rays: treatment of cancer
microwave: telephone communications; radiowaves: radio broadcasting
(vii) Infinite
(viii) We can get UV radiations from a mercury vapour lamp. Sun also produces UV rays
which is largely absorbed by the ozone layer. UV rays can cause damage to the skin.
SAQ 7:

(i) The statement is true. Their relation is E =

hc

(ii) x-ray photon is more energetic than IR photon, because the wavelengths of x-ray radiations are
smaller than IR radiations(Refer the electromagnetic spectrum) and energy is inversely proportional to
wavelength.
(iii) In electromagnetic spectrum, cosmic rays are most energetic as its wavelength is the shortest and
radiowaves are least energetic as its wavelength is the greatest.
(iv) Energy of a photon is directly proportional to wave-number. E = hc
(v) The statement is not true, because according to Planck's quantum theory, electromagnetic radiations
are not emitted or propagated in space continuously but take place in the form of discontinuous energy
packets called quanta or photons.
(vi) Because the photons are emitted and propagated so fast that the discontinuity is not noticed.
-27 10
6.627 X 10 X 3 X 10 -12
(vii) E = -8 = 2.84 X 10 erg
7000 X 10
-27 15 -12
(viii) E = 6.627 X 10 X 10 = 6.627 X 10 erg
 -27 10 -16
(ix) E = 6.627 X 10 X 3 X 10 X 1 = 1.98 X 10 erg

-27 10
-18
(x) E = hc ⇒ 1.98 X 10 =
6.627 X 10 X 3 X 10
 
⇒  = 100 cm
It belongs to the radiowaves region of the electromagnetic spectrum.
E = hν = 6.627 X 10-27 X ν = 1.98 X 10-18 erg.
⇒ ν = 2.98 X 108 sec-1
E = hc ⇒ 6.627 x 10-27 X 3 X 1010 X  = 1.98 X 10-18 erg.
⇒  = 0.01 cm-1
SAQ 8:
(i) White (ii)Violet and red colours respectively
(iii) No, this statement is incorrect. Green colour consists of a large number of waves having approximate
wavelength range of 5000-5500 Å. In the vicinity of 5000 Å, the green is mixed with faint blue as the green
colour comes just after blue colour. In the vicinity of 5500 Å green colour is mixed with faint yellow colour
as yellow colour comes just after green. Thus there is a continuity of colour throughout the
spectrum(VIBGYOR). Refer the picture of solar spectrum in the text.
(iv) Violet colour radiations have the shortest wavelengths and travel with minimum velocity in the prism
and hence is deviated to the maximum.
(v) Visible radiations have wavelengths greater than UV radiations and come just after it while x-rays
radiations have wavelengths smaller than UV radiations and come just before it.
(vi) No, we do not get any colour in any spectrum other than visible spectrum.
SAQ 9:
(i) Discontinuous
(ii) FALSE. We get individual lines which are well separated from each other.
(iii) FALSE. We get a band of seven colours having no gap in between.
SAQ 10:
(i) True
(ii) False: Solar spectrum is continuous while H-spectrum is discontinuous (line) spectrum.
(iii) Spectrometer is the instrument which separates a mixture of waves and disperses
them into pattern of waves with increasing wavelengths from bottom top. The simple
spectrometer consists of a prism and a photographic plate(screen).
SAQ 11:
(i) Emitted. (ii) Absorbed
(iii) (a)Yes. It will lose by an amount (q-p) joule and it will go to the first shell(K).
(b)No. It cannot go closer to nucleus than the K shell.
(c)Yes. It can lose (r-q)joule and go to L shell(2nd) and lose (r-p) joule to go to K shell.Thus there
are two possibilities.
(d)K shell. By absorbing it will go to L,M,N..... It cannot go closer to the nucleus, so will not emit
energy.
(e)There are six possible transitions: These are 4---->3, 4---->2, 4---->1, 3---->2, 3---->1 and
2---->1. The jump 4---->1 will emit greatest energy photon and 2---->1 will emit the least energy photon.
SAQ 12:
(i) When the electron is at infinite distance i.e when the electron is far away from the nucleus, the
energy of the electron is assumed to be zero. When it comes closer to the nucleus, it is more and more
attracted by the nucleus. Remember that whenever there is attraction, there is a net decrease or loss of
energy. The loss is associated with a negative sign. As the electron comes nearer to the nucleus its energy
becomes more and more negative as more and more energy is lost. Let us take one example. You have some
money with you which you declare to us to be zero rupee. Supposing you lose 500 rupees out of that. What
will be your wealth amount? It will be -500. Similarly if you lose 1000 rupees, your wealth value will be -
1000 and so on. Similarly as electron goes closer to nucleus it loses more and more energy and takes more
and more negative values. Numerically the value increases but as a whole the value decreases. When
electron reaches in the 1st shell from infinite distance, it has lost k(2.18× 10-11erg) amount of energy, so that
its energy in the 1st shell is -k. Similarly when electron comes from infinite distance to 2nd shell, it has lost
k/4 amount of energy, so that its energy in the 2nd is -k/4. Similarly, the energy in the third shell is -k/9 and
so on. I guess now you understand why the energy of the electron is negative.
(ii) In the example solved just before in the text, the photon absorbed when electron jumps from 1st to
2nd shell has a wavelength of 1216Å. So when it jumps from 2nd shell back to 1st shell, photon of same
value i.e 1256Å will be emitted.
(iii) Energy of electron in 3rd shell = E3 = - k/9 and in the first shell = E1= -k

So the difference = E = E3 - E1 = hc = -k/9 - (-k) = 8k/9


hc = 8k
⇒
 9
hc   .   erg. sec   cm / sec
⇒ λ   
 .   cm
k   .  erg
= 1.026 × 10 × 108 Å = 1026 Å.
-5

So the photon absorbed for the jump is 1060Å and it falls in the ultraviolet region of the electromagnetic
spectrum.
(iv) When electron jumps from 3rd shell back to 1st shell, photon of same wavelength that was absorbed
while jumping from 1st to 3rd shell i.e1060Å(SAQ iii) will be emitted.
(v) Energy of the electron in the 3rd shell = E3 = -k/9 and in the 2nd shell=E2= -k/4

So the difference = E = E4 - E2 = hc = -k/9 - (-k/4) = 5k/36


hc = 5k
⇒
 36
hc   .  erg. sec   cm / sec
⇒ λ   .  cm
k   .  erg
= 6.566 × 10-5 × 108 Å = 6566 Å. So the photon having wavelength of 6566Å is to be absorbed when
electron jumps from 2nd shell to 3rd shell. This photon belongs to the visible region(3800-7600Å)of the
electromagnetic spectrum.
If the electron jumps from 3rd shell back again to 2nd shell, then the photon of same wavelength i.e 6566Å
will be emitted out.
(vi) Energy of the electron in 6th shell= E6 = -k/36 and in the 3rd shell = E3 = -k/9. E6 is greater
than E3. As electron goes farther away from the nucleus to higher and higher shells, its energy value goes
on increasing.
(vii) The energy of the electron is zero at infinite distance and -k in the 1st shell. So the energy difference
= E∞ − Ε1 = 0 - (-k)= k
So k(2.11 X 10-11erg per atom) is required for the electron to jump from 1st shell to infinite distance.
(viii) The energy difference between E2 and E1 is less than between E3 and E1 which in turn less than
the energy difference between E4 and E1. As the energy of the photons go on increasing in the three jumps
mentioned, the wavelength will go on decreasing. This is because the energy is inversely proportional to
wavelength.
(ix) A girl was given a 18th century old child garment to mend for exhibition purpose. To her utter surprise
she found a 7" wide tucks of extra fabric in the shoulder and side seams. Then she realised the reason for
it. Since in those times material was valuable and never wasted and the dress was meant to last a lifetime,
and the extra cloth was added to allow the dress to grow with its wearer over the years. Unfortunately the
child wearing that dress might not have grown further or might have dead and it remained as such without
expanding. Same thing happened to the designation of K, L, M..... to the shells.
In early 20th century, x-rays were discovered by the bombardment of cathode rays on metals. Barkla
found two types of x-rays from metals- one was of more penetrating type called as K- radiation and the other
less penetrating type called the L-radiation. He anticipated that there might be still more penetrating x-rays
which will be discoverd later and so he started naming from the middle of alphabets. But unfortunately that
never happened. So the letters K, L remained as such and the shells were designated as K, L, M, N.....In
fact the most intense K- radiation (x-rays) are produced when electron from a metal is knocked from the
1st shell by electron beam and is again recaptured and L radiation(less intense) are produced when electron
is knocked out from 2nd shell and is then recaptured.
SAQ 13:
(i) (a)n=4 to n=2 (b) n=2 to n=1 (c) n=6 to n=3 (d) n=4 to n=1
(e)n=5 to n=2 (f)n=6 to n=4 (g)n=6 to n=5
(ii) ΔE = E3-E1 = -k/9 -(-k) = 8k/9 = hc/λ ⇒ λ = 1060 Å (UV)
(iii) ΔE = E5-E2 = -k/25 - (-k/4) = 21k/100 = hc/λ ⇒ λ = 4485 Å (Visible)
(iv) ΔE = E5-E3 = -k/25 - (-k/9) = 16k/225 = hc/λ ⇒ λ = 13246 Å (IR)
(v) Continuous or band spectrum. Actually the spectrum is a line spectrum.
SAQ 14:
(i) Electromagnetic waves do not carry any real material particles. They carry only energy packets(photons);
eg. UV, Visible, IR etc. Electron waves carry real material particles, like electron(microscopic),
bullet(macroscopic) etc. All electromagnetic waves travel with the same speed( 3 X 1010cm/sec) while
electron wave or any other matter waves can travel in any speed.
(ii) Orbital is the three dimensional space in which the electron possessing a particular energy value can
remain anywhere within it.
SAQ15:
(i) l value for any p-subshell is 1. (l=1)
(ii) 3rd shell has 3 subshells. The three l values are 0, 1 and 2 for s- , p- and d- subshells respectively.
(iii) n=2, for p-subshell l=1. Note that p-subshell is denoted by l=1 irrespective to which
shell it belongs.
(iv) The electron is present in the 4th shell(n=4) and f-subshell(l=3) of the 4th shell. Note that
the 4th shell has four subshells namely s-, p- , d- and f-subshells.
(v) p-subshell of second shell has n=2 and l=1 but the p-subshell of the third shell has n=3
and l=1. Although their l values are same, their n values are different. From this the two can be
distinguished.
(vi) n=5 and l=0. Note that for any s-orbital irrespective of the shell, the l value is 0.
(vii) The first electron will have n=4 and l=3 while the second electron will have n=5 and l=3.
Their principal quantum numbers(n) are different.
(viii) The 5th shell will have five subshells given by the l values 0, 1, 3 and 4 represented b y
the symbols, s, p, d, f and g respectively.
SAQ 16:
(i) 2p>2s (ii) No, The actual order is 3s<3p<3d
(iii) 4f (iv)In the 4th shell(N) and in its p subshell.
(v) No, the second shell(n=2) has two subshells represented by l=0(s) and l=1(p).
(vi) 2p has higher energy.
SAQ 17:
(i) m= -1, 0, +1. p-subshell contains three p orbitals
(ii) For l=2, five(2l+1) values of m are possible. They are: -2, -1, 0, +1, +2. There are five
d- orbitals.
(iii) s-subshell has only one orbital. The subshell itself is the orbital. For this, l=0 and m=0
(iv) For f-subshell, l=3 and for l=3, the values of m are: -3, -2, -1, 0, +1, +2 and +3. These
seven values represent seven f-orbitals.
SAQ 18:
(i) It is 3p orbital. We cannot say which orbital out of the three orbitals(px, py or pz) at this
level. The elctron is either spinning clockwise or anticlockwise.
(ii) It is in the 2s orbital.
(iii) It is the 2s subshell. An s-subshell has the l value=0, hence the m value given is not
possible.
(iv) NO. It is the 4d subshell which has m= -2, -1, 0, +1, +2. So the m value given is not
possible.
(v) n=4, l=0, m=0 and s = +½ or -½.
(vi) n=2, l=1, m = -1, 0 or +1 and s= +½ or -½.
(vii) n=3, l=2, m=-2, -1, 0, +1 or +2 and s=+½ or -½.
SAQ 19:
(i) The second electron has two options. One, it may go to a higher energy orbital, second it may remain
with the first electron in the same orbital with opposite spin with respect to the first electron. The first requires
more energy than the second option. So it remains in the same orbital.
(ii) The repulsion between the third electron with the electron pair already present in the orbital is
unfavourably high and requires more energy than if the third electron would have gone to a higher energy
orbital. Thus the third electron cannot stay in the same orbital and it goes to the next higher energy orbital.
SAQ 20:
(i) 2 X 52 = 50 elctrons
(ii) For p-subshell: l=1 and for this there are three m values: m= -1,0,+1 for three orbitals(px,
py and pz). Each orbital contain two electrons with s= +½ and -½. So in total the p- subshell will
contain 3X2=6 electrons.
(iii) A d-subshell can accommodate 10 electrons. The l value for the d -subshell = 2 and
there are five m- values(-2,-1,0,+1,+2) possible for it. The five m- values represent five
orbitals. Each orbital contains two electrons with s= +½ and -½. So the total electrons i n
the d-subshell= 2 X 5 =10
SAQ 21:

(i) The number of unpaired electrons: 3

3d7

(ii) The number of unpaired electrons: 3

p3
(iii) Four d orbitals will be singly occupied. The number of unpaired electrons:4
(iv) After filling seven f-orbitals with one electrons, the 8th, 9th and 10th electrons will pair
the three orbitals. Another four f-orbitals will contain 4 unpaired electrons. Do the box
diagram for yourself.
(v) Two unpaired electrons (vi) 4 unpaired electrons.
SAQ 22: Let us hypothetically imagine the following situation. If the two electrons in the neighbouring
degenerate orbitals would spin in opposite directions, they would develop some affinity towards each other.
This is due to the equal and opposite magnetic fields they produce. It may so happen that one electron may
leak or slip into the other room and the moment the two remain in one orbital rendering the other one vacant,
that becomes an unfavourable high energy situation as one orbital would lie vacant while the other orbital
having same energy would be occupied by two electrons. Thus one of the electrons from the pair would
immediately come back to the vacant orbital from which it slipped and now it would spin in the same direction
as the other one and not in the opposite spin as it did before. Thus we logically proved that all the unpaired
electrons in the degenerate orbitals spin in the same directions.
SAQ 23: The reader is advised to find the (n+l) values of the orbitals and check with the answers.
(i)4p<4d (ii)6s<4f (iii)5s<4f (iv)4p<5s(here n+l values are same)
(v)4f<5d(here also n+l values are same).
SAQ 24: The abbreviation UE has been used for Unpaired Electrons.
2
He(2):1s (No UE) Be(4):1s2,2s2(No UE);
2 2 1
B(5):1s ,2s ,2p (UE-1); C(6):1s ,2s22p2(UE-2)
2
2 2 4
O(8): 1s , 2s ,2p (UE-2) F(9):1s22s22p5(UE-1);
2 2 6
Ne(10): 1s ,2s ,2p (No UE) Mg(12):1s2,2s2,2p6,3s2(No UE)
2 2 6 2 1
Al(13): 1s ,2s ,2p ,3s ,3p (UE-1) Si(14): 1s2,2s2,2p6,3s2,3p2(UE-2)
P(15): 1s2,2s2,2p6,3s2,3p3(UE-3) S(16): 1s2,2s2,2p6,3s2,3p4(UE-2)
2 2 6 2 6
Ar(18): 1s ,2s ,2p ,3s ,3p (No UE) K(19): 1s2,2s2,2p6,3s2,3p6,4s1(UE-1)
2 2 6 2 6 2 1
Sc(21): 1s ,2s ,2p ,3s ,3p ,4s , 3d (UE-1) Ti(22): 1s2,2s2,2p6,3s2,3p6,4s2,3d2(UE-2)
2 2 6 2 6 2 3
V(23): 1s ,2s ,2p ,3s ,3p ,4s ,3d (UE-3) Mn(25):1s2,2s2,2p6,3s2,3p6,4s2,3d5((UE-5)
2 2 6 2 6 2 7
Co(27): 1s ,2s ,2p ,3s ,3p ,4s ,3d (UE-3) Ni(28): 1s2,2s2,2p6,3s2,3p6,4s2,3d8(UE-2)
2 2 6 2 6 2 10
Zn(30): 1s ,2s ,2p ,3s ,3p ,4s ,3d (No UE)
Br(35): 1s2,2s2,2p6,3s2,3p6,4s2,3d10,4p5(UE-1)
I(53): 1s2,2s2,2p6,3s2,3p6,4s2,3d10,4p6,5s2,4d10,5p5 (UE-1)
Sn(50): 1s2,2s2,2p6,3s2,3p6,4s2,3d10,4p6,5s2,4d10,5p2(UE-2)
Hg(80): 1s2,2s2,2p6,3s2,3p6,4s2,3d10,4p6,5s2,4d10,5p6,6s2,4f14,5d10(No UE)
The reader is advised to add the electrons present in all the subshells of each shell and write down the shell-
wise configuration. Let us take the case of Hg(80)
Hg(80): 2, 8, 18, 32, 18, 2
SAQ 25:
(i)No. of electrons=26-2=24: 1s2,2s2,2p6,3s23p64s03d6: 4 unpaired electrons.
Note that the two electrons lost from Fe atom to form Fe2+ goes from 4s, the valence shell(not 3d). So in
the configuration of Fe2+, 4s0 has been written. You can also delete 4s from the configuration.In all the
elements in the transition series given below(excepting S2-, which is not a transition element), first the
electronic configuration of the neutral atom is written, then the required number of electrons are removed
first from the 4s and then if required from 3d. Hund's rule is applied to the incomplete 3d subshell to find
the number of unpaired electrons.
(ii)No of electrons=16+2=18: 1s2,2s2,2p6,3s2,3p6: 0 unpaired electron
(iii)No. of electrons=24-3=21: 1s2,2s2,2p6,3s23p64s03d3 3 unpaired electrons
(iv)No. of electrons=29-1=28: 1s2,2s2,2p6,3s23p64s03d10 0 unpaired electron
2 2 6 2 6 0 10
(v)No. of electrons =30-2=28: 1s ,2s ,2p ,3s 3p 4s 3d 0 unpaired electron
SAQ 26:
(a) (i) 3d5 : UE = 5, so μ = √35 BM (ii) 3d10, UE = 0, μ = 0 (iii) 3d5, 4s1, UE = 6, μ =√48
(b) n(n+2) = 3.79 BM, n = 2.93 ≈ 3
SAQ 27: (i)isobars (ii)isotopes (iii)isotopes (iv)isotones (v)isobars (vi)isotones
 More on Schrodinger Wave Equation and Nodes
Stationary Wave : Vibration of a stretched string tied at two ends produces stationary waves.
d 2 4 2
Wave Eqation in one dimension :   
dx 2 2
ψ = displacement ( function of amplitude ) of wave at the point x
λ = wavelength of the wave
Solution of the above 2nd order differential equation results the following two ψ values - one real and other
complex. Solutions i.e ψ values are called " amplitude functions " .
 2x   2ix 
(Real)   A sin   (1) (Complex)   Be 

 

(2)
  
Verification :
Real

 2x 
  A sin  
  
d 2  2x 
  A cos 
dx    
d 2 4 2  2x  4 2
 2   2 A sin   2 
dx     
Complex :
 2ix 
 
  Be   

 2ix   2ix 
d  2i    d 2 4 2   4 2
   Be
 
 2   2 Be  
 
dx    dx  2
Wave Equation in one dimension:
d 2 4 2 4 2 m 2 v 2 8 2 mK E
 2     
dx 2  h2 h2
( λ = h/mv : de Broglie's equation and KE = Kinetic Energy = ½ mv2)
d 2 8 2 m( E  V )
    ( E = Total Energy, V = Potential energy)
dx 2 h2
Wave Equation in three dimension (Schrodinger's Equation) :
For three dimension, it will be a partial differential equation given below
 2  2  2 8 2 m( E  V )
     (1)
x 2 y 2 z 2 h2
Short Representation :
8 2 m( E  V ) 2 2 2
   where    
2 2
(Laplacian Operator)
h2 x 2 y 2 z 2
Rearrangement of equation (1), gives
 h2   2 2 2  
  
     V   E
2  (2)
 8 m  x y z 
2 2 2

But
1
2m

px  p y  pz  V  E
2 2 2
 (3)
where px, py and pz are the momentum of there components of the electron.
Comparing equation (2) with equation (3), we get,
1
2m
2 2 2

h2   2 2
8 m  x y
2 
px  p y  p z   2  2  2  2 
z 
(4)

The expression in LHS of equation (3) is called HAMILTONIAN. Hence the expression within the square
bracket in the LHS of equation (2) is called 'Hamiltonian Operator' ( H ) . Hence equation (2) can be written
as
H  E (5)

 h2   2 2 2  
Where H    
     V  , in which V respresents the operator for potential energy and
2 
 8 m  x y z 
2 2 2

the rest(bigger expression) is the operator for kinetic energy.
Graphs:
Each solution of Schordinger's wave equation for a particular set of n, l and m is called a
EIGENFUNCTION(ψ ψ) and respresents an ORBITAL.
In polar coordinates ( r ,θ, φ )

ψ(r,θ, φ ) = R (r) × θ (θ) × φ (φ)

R(r) gives the dependence of ψ upon distance from the nucleus while θ and φ give the angular dependence.
R(r) = Radial Wave Function ( H atom)

3
 Z  2  Zr  Zr
1s Orbital: R  2  e a0  K1s e a0
 a0 
3
 1  Z  2
 Zr   Zr  Zr   Zr
2s Orbital: R    2  e 2 a0  K 2 s  2  e 2 a0
 2 2  a0   a0   a0 
3
 1  Z  2
Zr  Zr 2 a0  Zr
2p Orbital: R   e  K 2 p re 2 a0
 2 6  a0  a0
a0 = 0.529 Å (52.9 pm).
R vs. r Graphs:

R2 Vs. r Graphs:
ψ or R has no physical significance. However R2 or ψ2 has a significance. R2 = Electron Probability
Density i.e probability of finding electron at a point or the probability of finding electron in a unit volume.
s orbital :That is, the electron will be detected close to the nucleus most frequently and the probability of
observing it at some distance from the nucleus will decrease rapidly with increasing r. The electron will appear
to be "smeared out" and we may interpret R2 as giving the fraction of the total electronic charge to be found in
every small volume element of space
(See later)
For s-orbitals, the maximum electron density is at the nucleus.All other orbitals have zero electron density at the
nucleus. This may not be confused with the fact that electron is present at the nucleus for s-orbital. This means
the electron density is highest surrounding near the nucleus.
Radial Probability Distribution Function(D):
D = 4πr2 R2

dV

r dr

D is the probility of finding electron in the layer(having volume dV) which extends from 'r' to 'r + dr ' .
D describes the manner in which the total electronic charge is distributed in space. We may determine the total
amount of charge lying within a thin spherical shell of space. Since the distribution is independent of direction,
consider adding up all the charge density which lies within a volume of space bounded by an inner sphere of
radius r and an outer concentric sphere with a radius only infinitesimally greater, say r + dr. The area of the inner
sphere is 4πr2 and the thickness of the shell is dr. Thus the volume of the shell is 4πr2 dr and the product of
this volume and the charge density R2, which is the charge per unit volume, is therefore the total amount of
electronic charge lying between the spheres of radius r and r + dr.
 4
V  r 3  dV  4r 2 dr  R 2 dV  4r 2 R 2 dr  Ddr
3
D vs. r Graphs:
(see later)
At nucleus ( r = 0) , D = 0 for all orbitals.
ANGULAR NODES:
s-orbital does not carry any angle term in its wavefunction, hence its angle idependent. However,
p, d and f orbitals are angle dependent as each of their wavefunction carries an angle term. This is not discussed
here.

Electron Density(R2) and Radial Probability Function(D):

R2 gives the probability of finding electron in a small volume element(say cubic volume element) at a
radial distance 'r' from nucleus. We say this approximately as the probability of finding electron at a point.

D gives the probability of find electron in a concentric spherical layer lying between radial distance 'r'
and (r+dr).
For 's' orbitals we say the electron density is maximum at the nucleus . What does it really mean ? The
electron is more likely is available nearer the nucleus than farther from it. The electron density is maximum
nearest to the nucleus and as we go farther away from nuclues, the electron density decreases. When we see
the 's' orbital simulation picture with 'dots' representing the electron density(R2 values), we find that it is most
dense near to the nucleus and gradually the density of 'dots' decreases with 'r'. Since the graph on extrapolation
to y-axis touches it at the highest value of R2, we often say the electron density is maxium at the nuclues. This
statement is really not true. The electron density is maximum nearest to the nucleus.
When one takes the total electron density in the spherical layer(volume dV) for finding D, it will be found that
it is minimum at(nearest) the nuclues(i.e zero at the nuclues) and at certain intermediate radial distance(the most
probable radial distance(representing the principal maximum, which is multiples of a0) the D is maximum and
beyond that r the total electron density(D) again decreases as the electron density is greately decreased. With
increase 'r' the total volume of the sphereical space increases and total probability increases to a maximum.
With further increase in 'r' it again decreases due to sharp decrease in electron density although total volume of
the spherical space increases.
For a p, d or f orbitals, R2 is also zero like D at the nuclues. Since there is/are angular node(s) in these
orbitals passing through the nuclues, the electron density increases with radial distance to a maximum and
thereafter decreases like D.
 Black Body Radiation
An ideal body which absorbs all radiations incident upon it and reflects none and hence appear black
- is called BLACK BODY. It is an opaque and non-reflective body. Practically there is no perfect black body.
Graphite(an allotrope of carbon) and lamp black absorb 97% of radiations and hence are good approximations
of black bodies. A black body is not only an ideal absorber but also an ideal emitter- as it emits all wavelengths
of radiation. At a particular temperature it emits the maximum amount of energy possible for that temperature.
All objects above absolute zero emit radiations. A closed hollow box having graphite wall with a small opening
- when heated and its temperature is raised can be considered as an approximate black body. The simplest
example of black body radiator is a furnace which produces radiations which excape from a hole present in the
furnace. The emission curve(called the spectrum) of
the radiations at each temperature is determined in a
spectrophotometer. The emission curve of a black
body is unique for a given temperature which give
characteristic radiations at all wavelenghts(x-axis) with
their respective fixed intensities i.e the power
radiated(y-axis) at that temperature. The curve varies
with temperature. Intensity versus wavelength emission
spectra have maxima point for each temperature which
shifts to lower wavelength(higher energy) as
temperature increases. In other words the λmax moves
from IR to visible and then to UV.
The emission spectrum consists of a broad range of
wavelengths described by a distribution curve
A black body at room temperature appears black, as
most of the energy it radiates is infra-red and cannot be perceived
by the human eye. At higher temperatures(>5000C) black bodies
emit visible radiations and glow with increasing intensity and colors
that range from dull red, then to yellow and finally to blindingly brilliant
blue-white as the temperature increases. Hence the slogan " The
hotter the object, the "bluer" the light it emits".
At 6000K, it looks white. Wien's law gives the wavelength at the
maxium intensity at each temperature(called λmax) while Stefan-
Boltzmann law gives the power(total power- not the power at each
wavelength) of radiation.
Wien’s Law : λ(max) in m = (2.898 X 10–3)/T
Stefan-Boltzmann Law : P = σ A T4
P = total power in Watts,
σ = Stefan-Boltzmann constant Constant
= 5.67 x 10-8 W m-2 K–4
A = surface area in m2.
There is a distribution of energy(wavelength) at each temperature analogous to velocity distribution of gaseous
molecules at fixed temperature(Boltzmann distrubution). In this case, small number of particles of the black
body are radiating low energy(to the right of maxmimu point of each graph) and also small number of particles
radiating very high energy(to the left of the maximum point). But maximum number of particles are radiating
intermediate energy at or near the λmax value. The area under each curve gives the total energy emitted by the
black body. Note that the total area under the curve increases(unlike velocity distribution in gas molecules) as

the temperature increases, indicating that the hotter an object is, the more energy it radiates.
The emission curves(spectra) in black body radiation could not be explained by classical laws of equipartition
of energy given by Raleigh-Jean law, particularly at lower wavelengths.
Where ρ = spectral enegy density i.e the energy emitted by unit volume of emitter( equivalent to intensity
represented by y-axis of the emission curve), T is absolute tempeture and λ = wavelength and k= Boltzmann
constant (R/NA)
This law failed at lower wavelength(higher energy). According to this law, the intensity of radiation should go
on increasing with decrease in wavelength, which was not the acutal case. There is always a Boltzmann distribution
of energy(wavelength) for all emitting bodies. This failure was called ultraviolet catastrophy as the law failed
when the radiation proceed towards the UV region. Thus Raleigh-Jean law was rejected.
Planck's Quantum Theory:
Max Planck proposed that energy is emitted/absorbed in the discrete energy packets as whole number of
multiple of hν. (E = n hν = nhc/λ, where n = 1, 2, 3…….) i.e energy absorption and emission are quantized.
Where is the ν = freqency and λ = wavelength.
• Energy photons are emitted from the black body when the atoms of the body vibrate and exchange
energy between them for which atoms attain different excited vibrational states and the electrons also attain
different excited electronic states(infinite number of states). These are called oscillators(atoms/molecules/
electrons). When they return back to ground or lower states, they emit photons of all possible frequencies or
wavelengths.
* Therefore, the spectrum is a continuous one, meaning that all wavelengths are emitted, although with
intensities that vary smoothly with wavelength. The other curious property of black body radiation is that it is
independent of the composition of the object; all that is important is the temperature.
* In 1900, the great German physicist Max Planck showed that the shape of the observed spectrum
could be exactly predicted if the energies emitted or absorbed by each oscillator were restricted to integral
values of hν, (E = nhν ). The allowable energies of each oscillator are quantized, but the emission spectrum of
the body remains continuous because of differences in frequency among the uncountable numbers of oscillators
it contains.This modification of classical theory, the first use of the quantum concept, was as unprecedented as
it was simple, and it set the stage for the development of modern quantum theory.
• When wavelength is very high i.e energy small, the number oscillators attaining to that low energy
state is small as even at ordinary temperature, the vibrational quantum levels are moderately high. Hence the
number of photons emitted is less and hence intensity of radiation is low.
• Intensity is directly proportional to the number of photons emitted and hence to the probability of the
number of oscillators attaining that quantum level

• As the wavelength decreases(energy increases), more and more number of oscillators attain those
quantum levels and hence number of photons emitted becomes more. Thus intensity increases to a maximum
(corressponding to λmax).
• At still lower wavelength(energy is still more), the number of oscillators attaining to that high quantum
levels becomes less and hence the intensity decreases as wavelength decreases more and more.
• Planck proposed a new law for finding spectral energy density(intensity) which fitted well to the
experimental curves(Plack's Distribution Law) by using his quantum theory given before.
h=Planck's constant, c= 3 X 108 m/s. and k = Boltzmann constant.
• Increasing the temperature shifts the λmax to lower values with increase in intensity as the number of
oscillators attaining higher quantum levels become more (increase in intensity) as well as the energy of the
quantum level(most probable) also increases(decrease in λmax )
• The area under the curve increases as the total energy emitted per unit volume of the black body
increases. With increase in temperature the number of atoms attaining each quantum level increases and hence
their intensities.
N.B . (1)Black holes are nearly perfect black bodies. Sun is also an approximately blackbody(effective temperature
of 5800K)
(2) Black body radiation is also called Thermal radiation or Temperature radiation or Cavity radiation.
(3) The spectral energy density or intensity of emission does not depend on the structure, shape and
nature of material of the body.
(4) Sun emits 160,000 times more energy than earth(Enegy varies as fourth power of T). The temp. of
earth is 280K. Earth emits mostly IR radiations while sun emits mostly visible radiation.
(5) Stars and planets can be called approximate black bodies.
(6) Blackbody radiation" or "cavity radiation" refers to an object or system which absorbs all radiation
incident upon it and re-radiates energy which is characteristic distribution of energy photons dependent on
temperature only, not dependent upon the type and intensity of radiation which is incident upon it.
Einstein Theory of Relativity
Einstein showed that the velocity of light, unlike that of a material body, has the same value no matter what
velocity the observer has. Further, the mass of any material object, which had previously been regarded as an
absolute, is itself a function of the velocity of the body relative to that of the observer (hence "relativity"), the
relation being given by
m0
m
2
1 v
c2

in which m0 is the rest mass of the particle, v is its velocity with respect to the observer, and c is the velocity of
light.

According to this formula, the mass of an object increases without limit as the velocity approaches that of light.
Where does the increased mass come from? Einstein's answer was that the increased mass is that of the kinetic
energy of the object; that is, energy itself has mass, so that mass and energy are equivalent according to the
famous formula
E = mc2 Truly : E = mrel c2

The only particle that can move at the velocity of light is the photon itself, due to its zero rest mass. But it will
have an effective mass and hence momentum while in motion which are given by

E h h
m  2 
c 2
c c
h
hence Momentum  mc 

(Remeber this is the same as de Broglie equation - except c is replaced by v of material particle)

Einstein's Original Equation: E2 = p2c2 + mrest2c4

This is applicable for both material particle having nonzero rest mass and photons having zero rest mass. For
photon : E = pc = mrel c2
So photon has momentum but no real mass. It is effective mass. Its energy content can be seen in terms of mass
due to mass-energy equivalence. Its not the true mass. Photon cannot remain static so there is no question of
measuring its rest mass. Moreover it has been arbitrarily taken as zero as only particles(photons) having zero
rest mass can take the velocity 'c'. Particles with nonzero rest mass cannot acquire 'c'. Its relativisitic mass
tends to infinity as its velocity approaches 'c'. This is because the increased kinetic energy which is equivalent
to its mass. This is relativistic mass and not the invariant mass.
* E = 1/2 mv2 work for particles having nonzero rest mass having velocity much less than 'c'.
* E = mc2 work for particles having nonzero mass moving with velocity close to 'c' and for
particles(photons) having zero rest mass.
At rest, E0 = m0c2. Rest energy is equivalent to rest mass(also called the inertial mass)
While ET = mrel c2. ET is the total energy object in motion and mrel is the total mass(relativistic mass). This mass
is not much different from rest mass at lower speeds but when speed approaches 'c', its relativistic mass
becomes very large.
Relativistic mass: the object moves at a constant speed relative to the observer. Hence the term.
Adding 25 KWh(90 MJ) of energy in any form to any object increases its mass by 1μg.
Penetrating and Screening Effects:
Penetration describes the proximity to which an electron can approach to the nucleus. In a multi-electron
system, electron penetration is defined by an electron's relative electron density (probability density) near the
nucleus of an atom. Electrons in different orbitals have different wavefunctions and therefore different radial
distributions and probabilities (defined by quantum numbers n and l around the nucleus). In other words,
penetration depends on the shell (n) and subshell (l). For example, we see that since a 2s electron has more
electron density near the nucleus(one subsidiary maximum and one node) than a 2p electron(no node), it is
penetrating the nucleus of the atom more than the 2p electron. The penetration power of an electron, in a multi-
electron atom, is dependent on the values of both the shell and subshell.
If you look to the D vs. r graph of 3s, 3p and 3d orbitals, 3s orbitals have more electron density closer to the
nucleus as it has two subsidiary maxima with two nodes. 3p has one subsidiary maximum with one node and
hence has lesser electron density closer to nucleus than 3s orbital. 3d orbital has no node and has least electron
density nearer to the nucleus. Hence the order of penetration : 3s > 3p > 3d.
Similarly we can understand for n = 4, the penetration order is : 4s > 4p > 4d > 4f
More the penetration of an orbital, more is the nuclear attraction and hence less is the energy.

In fact, the (n+l) rule or the aufbau principle is based on the relatie penetration power. Penentration power
among all orbitals is
1s>2s>2p>3s>3p>4s>3d>4p>5s>4d>5p>6s>4f....
hence the energy order is just the opposite.
1s<2s<2p<3s<3p<4s<3d<4p<5s<4d<5p<6s<4f.......

Greater an orbital penetrates towards the nucleus, greater it can shield outer electrons from getting the feel of
the nucleus. The order is the same.
3s > 3p > 3d
A 3s electron shields an outer electron say, a 4s electron better than 3p, which in turn shields better than 3d.
Due to shielding or screening of innter elctrons, the outer electron does not get the feel of all the protons the
nucleus is carrying. In other words, the +ve charge actually present inside the nucleus is nullifed by the inner
electrons and effective nuclear charge the outer electron experience is much less than the actual charge. Shielding
arises actually due to repulsion between the inner electrons and the outer electron which reduces the force of
attraction. The nueclear charge is actually not neutralised by the inner electrons, it appears to be neutralised due
to the repulsion effect.
Discovery of Electron by JJ Thomson(Determination of e/m ratio of electron)

1. In CRT(formerly called Crook’s discharge tube) at normal pressure, air(gas) is poor conductor of
electricity even at high voltage(10,000V) due to resistance of air particles.
2. At 10–3 atm(0.76 mm of Hg) air
conducts electricity and it pinkish
GLOWS(positive column). This is due to
SLOW Diffusion mechanism. Gas molecules
at this pressure, become spontaneously
positive ions by losing electrons(PLASMA
state). The electron jumps from one neutral
atom to the other +ve ion resulting the glow.
As pressure reduced, Faraday’s and Crook’s dark spaces are created
in front of cathode and it extends as pressure is further lowered.
3. At 10–6 to 8X 10–8 atm, the glow by gas stops(space between
cathode and anode becomes totally dark) and glass on the opposite
side(coated with flourescent material i.e ZnS) glows due to formation
of CATHODE rays(travel from cathode to anode).
The few positive ions strike on the cathode plate to extract a large
number of electrons from its surface which neutralise the ions and rest
proceed as cathode rays. Again the gaseous atoms lose electron
spontaneously(plasma state) and strike on cathode plate and extract
large electrons. This continues cyclically to sustain the cathode rays.
4. At 10–9 atm, the conduction stops. This proves that the residual gas molecules were responsible for the
generation of cathode rays. However in vacuum tubes with this pressure or lower, tungsten filaments are used
as cathode and heated to produce cathode rays(thermoionic emission).

Properties of Cathode Rays:

1. Kinetic Energy: Cause paddle wheel to rotate.
2. Negatively charge particles: Deflected to +ve plate of an electric field.
3. Deflected towards the north pole of a magnetic field taking a circular path.
4. Rectilinear motion: produced shadow of the object
Determination of charge to mass ration(e/m ratio)
The cathode rays were first subjected to an electric field to produce acceleration and then attain a
constant terminal velocity(v).
Then the beam is allowed to enter a magnetic field with constant velocity v. The beam bends with a
radius, r.
Electric Field:
1 2
mv  qV (1)
2
(where V = PD of the electric field, q = charge of electron, m = mass of
electron, v=velocity of electgron)
2qV
v2  (2)
m
Magnetic Fied:
mv 2
qvB = qvB  (3)
r
Where B = strength of the magnetic field,
(mv2)/r = centrefugal force for cicular motion), r = radius of the circular path
 q 2 B 2r 2
From eqn. (3) we get, v2  (4)
m2
From eqns (2) and (4), we get
q 2V
 2 2 (5)
m B r

Alternative Method:
First magnetic field was applied and deflection was balanced by electric field after that, so that the cathode
rays do not deviate.
qvB = q E (6)
E2
So v  2
2
(7)
B
From equation (4) and (7) we get
q E
 2 (8)
m rB

Discovery of Proton:
Eugen Goldstein discovered proton in 1886, but it was named in 1919 by Rutherford
* Goldsten used perforated cathode at air pressure of 1.3 X 10–6 atm(10,000V). Reddish glow was
observed at the back of cathode and also glow from glass at the back. These were called CANAL or
ANODE rays.
* These consisted of positively charged ions produced from the gas molecules/atoms.
* Rectilinear Motion * Deflected towards the negative plate of electric field.
* Charge to mass ratio(q/m) was different for different gases but independent of anode material.
* q/m ratio was maximum when hydrogen gas was taken .(q/m = 9.592 X 104 C/g)
* Charge of the particle was found to same as electron. Mass was 1836 times greater than electron.
* The positive ion from hydrogen gas was named as PROTON, a fundamental particle.
* For other gases, q/m ration were less. The masses were found to be multiple of proton’s mass. For
Oxgen it was found to be 16 times that of proton. When atomic number was discovered later to be 8, then it
was almost certain that where were 8 more neutral particles of similar mass as proton in O atom. This was later
named as NEUTRONs.
* Further confirmation came from nuclear transmutation reaction when alpha particle (He++) was allowed
to fuse with nitrogen atom, a neutral particle having similar mass as proton was produced and nitrogen atom
was transumted to F(17) isotope.
Discovery of Neutron:
Chadwick discovered netron in 1932. It was known long since that nucleus contains neutral particles
as there was mismatch between atomic number and atomic mass. But experimental evidence was lacking.
Chadwick confirmed it by the folollowing experiment.
Be 24He126 C  01n
9
4

When alpha particles were hit on beryllium metal, neutrons were produced and Be converted to C.
Determination of Charge of Electron by Millikan Oil Drop Experiment:
Parts of the Experimental Set-Up
1. Atomizer(Oil Sprying part) 2. X-Rays Source(Ionizing radiation)
3. Travelling Microscope 4. Charged Metal plates
5. Source of EMF

Absence of Electric Field:

* A fine mist of oil was sprayed into the upper chamber with an
atomizer.
* Some microscopic oil droplets passed through the small hole
on the upper +ve plate of the electric field.
* After short time of acceleration, the droplet acquires constant
speed inside the plates(terminal velocity) due to balancing of
gravitational force with viscous force(frictional force between fluid
layers) exerted by air to the oil droplet in opposite direction of the
motion. (Intertia of motion continues with constant velocity u1)
(Note when acceleration is not happening and the opposing force balances then the body moves with constant
velocity due to inertia of motion)
* This u1 is measured through travelling microscope.
* Gravitational Force(FG) = Mg = (4/3)πr3ρ g ............(1)
(where ρ = density of oil and r = radius of the spherical oil droplet.)
More correctly the net Gravitation Force(GF) = Mg - Bouyant force = (4/3)πr3(ρ-ρair)g ...........(2)
If the pressure of residual air is very small then we can neglect it and take equation (1), otherwise (2).
* Stoke’s law : The viscous force (FV) = 6πηru1 (3) (acting upwards)
(Where η = coefficient of viscosity of air)
* When droplet moving with constant speed downwards, then FG = FV
4 3 9u1
r (    air ) g  6ru1 ⇒ r2 
3 2 g    air  ...........(4)

From eqn. (4), radius of the oil droplet was determined.

Presence of Electric Field and Gas Ionized:

* Millikan used a X-Ray Source to ionize the air molecules and the ejected electrons captured by the oil
droplets. Varying numbers of electrons got captured by oil droplets making them negatively charged.
* Then electric field was applied by using a source of EMF.
* As the voltage across the plates increased, the velocity of the droplet in between the plates decreased
and at some optimum voltage, the droplet’s motion could be totally halted(stopped) i.e suspended.
* If the applied voltage is more than the optimum voltage for suspension, then there is upward movement
of the oil droplet with constant velocity u2. This is due to the balance of applied electric force acting upwards
and the net force acting downwards( sum of gravitational force and viscous force now acting downwards due
to upward movement of the droplet)
* Charge of oil droplets could be calculated either by SUSPENSION method or UPWARD MOTION
method.
Case-I : Suspension Method:
V
Electric Force (FE) = E × q ......(5) (Where E = Electric Field =
)
d
Where V = Voltage across the plates and d = distance between the plates
FG=FV = FE (6)
V 6ru1d
6 ru1  q  E  q  ⇒ q .........(7)
d V
All quantities are known so charge present in the oil droplets could be determined.

Case-II: When droplet moving upwards with constant velocity (u2)

* At this condition, the force acting upwards is FE’ and the forces acting downwards are gravitational
force(FG) and viscous force(FV’) due to upward motion(viscous force acts always opposite to the direction of
motion)
FE = E’ × q = FG + FV’ ...... (8)
q  E '  6ru1  6ru 2 ...................(9)


d 6ru1  6ru 2
q
 .................(10)
V'
Where V’ the voltage required for the upward motion of the droplet.

Calculation of charge of electron:

* The charge(q) were determined for a large number of droplets and found that the minimum difference
between them was 160.2 zC (zepto coulomb) = 160.2 × 10–21 C = 1.602 × 10–19 C
* In otherwords the charge in droplets were found to be whole number multiples of 1.602 × 10–19 C.
Hence the charge of each electron was found to be 1.602 × 10–19 C.

ZEEMAN EFFECT:
When the radiating sample is placed inside an external magnetic field and the radiation is
analysed through a spectrometer, each spectral line is split into a few finer lines(multiplet). This is Zeeman
effect. If electric field is used, it is called Stark effect.
Weak Magnetic Field : Zeeman Effect : (a) Normal and (b) Anomalougs Zeemam Effect.
Strong magnetic Field : Paschen-Back Effect.
In fact, the 3D natureof electron's orbit(orbital) and the possibility of having more than one orientations of
electron's orbital was strongly anticipated from Zeeman effect which led to the HUP and onset of QM.
Normal Zeeman Effect : When the net spin is zero(S =0), this is observed. When all the electrons are paired
in orbitals and there is no unpaired electron eg. in Mg, Zn, He etc, we observe normal Zeeman effect. In this
case, only the orbital angular momentum interacts with the external field. The electron spin does not contribute
to splitting of levels.
Supposing in Be atom whose net spin =0, one electron is excited from 2s to 2p level. The line due to
2p → 2s transition is a single line(singlet) in the absence of magnetic field. But in the presence of magnetic field,
the 2p orbitals become non-degenerate and split into three (2l+1) energy levels (ml = +1, 0, –1). One transition
in the absence of magnetic field is now converted to three transitions. 2p–1 → 2s; 2p0 → 2s and 2p+1
→ 2s. Hence three finer lines appear in place of single line. Thie is called a triplet. In this case electron spin does
not further split the lines, as the net spin=0. The electron going to the 2p level continues to remain in paired
configuration(called the singlet state) and cannot interact with external field and hence cannot further split the
energy levels.
Anomalous Zeeman Effect: When net spin is non-zero(S ≠ 0) i.e the atom has an one or more unpaired
electron, the orbital angular momentum vector(L) couples with spin angular momentum(S) vector to give a
resultant vector (J) which interacts with external field. This is called spin-orbit coupling or L-S coupling to give
the resultant vector J.
  
J  LS
The coupling of electron spin produces additional splitting of lines.
For example; Sodium has one unpaired electron in 3s orbital. In the absence of magentic field, it gives two
lines(doublet) D1 and D2 lines(explained later) at 5890 and 5896 Å. In the presence of magnetic field, D1 line
is split into 4 finer lines and D2 line split into 6 finer lines, a total of ten lines for the doublet. This is due to L-S
coupling for which additional splitting occurs(explained later)
Selection Rule:
Some transitions between two levels are not allowed. They are forbidden due to probability
considerations and hence such transitions will not result any detectable spectrall lines.
l  1 (allowed) and ml  0,1 (allowed)
As many number of allowed transitions of different energies will be there, same number of finer lines will appear
in the multiplet.
Zeeman Effect in Hydrogen Spectrum:
Although the case of hydrogen comes under anomalous Zeeman effect, Zeeman himself never knew about it in
the beginning. He used external magnetic field and took the spectrum under ordinary resolution(not high resolution).
Hence the fine structure due to spin-orbit coupling was not observed.
Normal Zeeman Effect for hydrogen:
Examples:
1. Under such conditions, he found that the first line of Balmer series (n= 3 to n=2) is split into three
equally spaced finer lines(triplet). It is due to transitions from five 3d orbitals to three 2p orbitals.There are nine
allowed transitions(others were forbidden according to selection rule) which give rise only 3 different transition
energies, as 6 others belonged to these three. This is because the the levels beween the orbitals are equally
spaced(gap is same) irrespective of the principal quantum number. Note that in H atom the all the subshells
belonging to a particular principal level are degenerate. Hence electronic transition can occur between principal
levels(not sublevels eg 3p to 3s as we find for the spectrum of Na, a many-electron atom). But in the presence
of external magnetic field the orbitals belonging to a subshell become non-degenerate and responsible for
splitting of line. Note that the transion from 3s to 2s (Δl =0) is forbidden. The transitions from 3p to 2s is
allowed(Δl = –1). The has three transitions as 3p orbitals(px, py and pz) are non-degnerate. But these three
transions match with the 3 transition already explained due to 3d to 2p. The transitions from 3d to 2s (Δl=2)
and 3p to 2p(Δl=0) are not allowed.

2. The 1st line for the Lyman series from n =2 to n =1 under external field was split into three line due to
transitions from 2px, 2py and 2pz orbitals to 1s orbital requiring three different transition energies.

(absorption shown, emision is its opposite)

Anomalous Zeeman Effect
1. Hydrogen: Under high resolution spetrometry and using external magnetic field for the radiating
hydrogen, further splitting of lines were obserbed due to spin-orbit coupling.
For the first line of Balmer series which was a triplet under ordinary resolution(normal Zeeman) will further split
into many finer lines, as each orbital will further split to two spin states(spin up and spin down). Hence many
more transitions will be taking place and hence furhter splitting lines occur. Same is case with the triplet of first
line of lymans series. Note that in this case, the s-orbital which was having degenerate spin states in the absence
of external magnetic field, will split into two spin states in the presence of external magnetic field. So additonal
splitting will occur due to it.
2. D-lines of Sodium: The anomalous Zeeman Effect is best understood from Sodium spectrum.

The LHS figure gives the formation of D1 and D2 lines of sodium in the absence of external magnetic field(Internal
Zeeman Effect: see later) and RHS figure gives the anomalous Zeeman effect under the presence of external
magnetic field. Note that spin-oribt interaction occurs for Na under ordinary resolution in the absence of
magnetic field and hence spin-orbit coupling occurs in the presence of magnetic field to result anomalous
Zeeman effect even under ordinary resolution.
Explanation of LHS figure:
The combination of orbital quantum number and spin quantum number (l ± s) is called j.
j=l±s
For 3p orbitals which are degenerate in the absence of magnetic field, there are two states denoted by (l+s)
3 1
and (l–s) i.e and which have been desigated as P3 2 and P12 in the figure. The lower 3s has one
2 2
state(degenerate spin states in the absence of external field as the for s-ortibal, the orbial magnetic dipole
moment is zero) So we get two lines of Na .
Explanation of RHS figure:
Since the degeneracy of three 3p-orbitals is lifted in the presence of external field and
additionally each level will have two spin states(up and down), there will be a total of 6 sublevels in stead of
two as found for the LHS figure. More correctly each of the sublevlels in the absence of external field i.e P3 2

and P12 will be split into (2j+1) number of sub-sublevels from +j to –j with increment of 1. So P3 2 sublevel

3 1 1 3 1 1
splits into  , , , (four subsub levels) and P12 level splits into  , (two subsub levles). Again
2 2 2 2 2 2
1 1
the 3s orbital is split into two sublevels due to the nondegeneracy of the two spin states(  , ). Thus now
2 2
 1 1
D1 line now splits into four lines due to transitions from the two lower 3p subsublevels(  , ) to the two 3s
2 2
3 1 1 3
sublevels and D2 line splits into 6 lines due to transitions from four higher 3p subsublevels(  , , , )
2 2 2 2
to the two 3s sublevels. So altogether 10 lines appear for two lines.

Internal Zeeman Effect(Fine Structure in spectra) : Spin-Orbit Interaction:

In the absence of external magnetic field and using high resolution spectrometer, it was found that each spectral
line was split into two finer lines due to two spin states(spin-up and spin-down) for the elctron. In the absence
1 1
of external magnetic field, there can be a splitting of the spin state into two energy levels(  , ) by the
2 2
interaction of the magnetic field generated due to orbital momentum. For any s-orbital (l =0), the angular
momentum of orbital is zero. Hence the two spin states of electron are degenerate. But for p-orbitals, although
the three orbitals are degenerate in the absence of external magnetic field, it has got a nonzero orbital angular
momentum and hence magnetic moment. This causes the degeneracy of the spin states to be lifted up. There
are two energy states(spin-up and spin-down). Thus splitting of spectral line into a doublet occurs.
Examples:
(1) In the Balmer series of H-spectra, the first red line due to transition from n =3 to n =2 in ordinary resolution
spectrum is split into a doublet in high resolution spectrum. This is due to transition of electron from 3s
orbital(degenerate spin states) to two non-degenerate spin-states of 2p state. Note that the transion from two
states of 3p to one state of 2s give the same two lines as the gaps between the sub state levels in p-state is same
in all the principal energy levels.
(2) Similary the first line of Lyman series in UV region splits into a doublet in high resolution. This is analogous
to D lines of sodium under ordinary conditions.

(2) The two lines D1 and D2 of Sodium even under ordinary resolution is due to spin-oribt interaction. When 3s
electron goes to 3p state and again returns back, gives the yellow radiations. Note that the gap between 3s and
3p is appreciable enough for electronic transition involving visible radiation. The two spin states of 3p
3 1
( and ) to 3s(single spin state) gives rise to the two lines. These two lines further split into further finer lines
2 2
in the presence of external magnetic field(anomalous Zeeman effect). This has been explained before.
Sommerfeld Model of Atom:
* To explain the fine structure(multiplet) in H-spectrum in the presence of external magnetic field(Zeeman
Effect), Sommerfeld proposed that the electron revolves in elliptial path alongwith cricular path.
* A single stationary state is converted to n-fold non-degenerate state in the presence of magnetic field.
For n=1(K shell), only one energy state(circular orbit), for n =2(L-shell) becomes 2-fold non-degenerate
states (one elliptical and the other circular), for n =3(M-shell), 3-fold non-degenerate(two ellipitical orbits and
one circular orbit) and for n=4(N-shell) 4-fold non-degenerate states( 3 elliptical and one circular) and so on.
* For example, the first line of Balmer series n=3 to n =2, will now have 6 possible transions from 3-
nondegenerate 3rd shell to 2-nondegenerate 2nd shell. Hence a single line splits into a few fner lines.
* The nucleus is located in one of the foci of the ellipse.]

The tangential velocity is resolved into two components , Vr(radial velocity) and Va(anglular velocity/transverse
velcity). Each component has its angular momentum component which is quantized.

h
Radial Angular Momentum =  nr  nr h
2
h
Angular Angular Momentum =  n  n h
2
Principal Quantum Number(n) = nr + nφ
Where nr = radial quantum number ; nφ= azimuthal quantum number(k)
Both nr and nφ = 1, 2, 3,......... (nφ is also designated as 'k' in many texts)
n length of major axis

n length of minor axis
When n = nφ, the ellipse becomes a circle.
* For n =1, nφ = 1, So K-shell is circular. (nr = 0)
* For n =2; nφ = 1,2 (two values); When nφ = 1, the orbit is Ellipital and for nφ = 2, the orbit is Circular
(So L shell has two sub-orbits : one elliptial and one circular)
* For n =3, nφ = 1,2,3 (three values), When nφ = 1 and 2; the orbits are Ellipital and for nφ = 3, the orbit
is Circular
(So M shell has three sub-orbitrs : two elliptical and one circular)
* For n = 4, nφ = 1,2,3 4(four values); When nφ = 1, 2 and 3; the orbits are Ellipital and for nφ = 4, the
orbit is Circular
(So N shell has four sub-orbits : three elliptical and one circular)
and so on.
Explanation of spectral fine Lines:
In the absence of magnetic field, the energy of electron is given by

 1  Z e
2
2 2
E    ( e= electronic charge; Z=atomic number
 4  2n h
2 2

me mn

me  mn = reduced mass of the atom, me = mass of electron, mN = mass of nucleus
For same n, but different nφ, the sub-orbits are degenerate.
In the presence of magnetic field, degeneracy is lifted due to relativistic effects and energy is given by

Z 2e 4   2Z 2  1 
E 1    3 
4 2 2n 2 h 2  n  n 4n 

1 e2 1
Where α = Fine structure Constant =  
4 hc 137
The selection rule for transition followed was as follows.
n (initial )  n ( final )  1
This could explain the fine lines in Zeeman effect to some extent. The full explanation came from Quantum
mechancal model of atom.