+Atomic structure and Wave Mechanics

Atomic structure: Atoms are made up of essentially three fundamental subatomic particles
electron, proton and neutron. A comparative study of these particles is given in the table below:

Electron Proton Neutron

Charge Negative, Positive, Neutral
1.6x10-19Coulomb 1.6x10-19Coulomb
Mass 9.11x10-31 kg 1.6725x10-27 kg 1.675x10-27 kg
Discoverer Joseph John Thomson, Ernest Rutherford, James
1896 1911 Chadwick1932
Experiment Passing electric Bombardment of Gold Bombardment of
discharge through gasses foil by α particle. Be by α particle.
at low pressure.

Bohr’s model
Niels Bohr extended the Rutherford’s model of the atom, he retained the nucleus of the atom and
proposed in addition that there are electrons moving in a circular orbit around the nucleus
obeying certain conditions e.g.; in hydrogen atom, Bohr proposed the nucleus contains one
proton with an electron revolving around it. Bohr proposed few postulates in order to rationalize:

1) An electron can revolve around the nucleus in certain fixed orbits of definite energy
without emission of any radiant energy. Such orbits are called stationary orbits. The radius of
such orbit is
𝒏𝟐 𝒉𝟐
r= which is 52.9×10-12 m for H-atom in the ground state.
𝟒𝝅𝟐 𝒎𝒁𝒆𝟐

2) An electron can make a transition from a stationary state of higher energy E 2 to a state of
lower energy E1 and in doing so, it emits a single photon of frequency,
𝑬𝟐 − 𝑬𝟏
=
𝒉
Conversely, E2−E1 = hν, where the energy of the radiation hν being equal to the energy
difference between the stationary states.
This is basically what was said by Max Planck’ (1905) statement: atoms and molecules could
emit (or absorb) energy only in discrete quantities, like small packages or bundles. Planck gave
the name quantum (plural quanta) to the smallest quantity of energy that can be emitted (or
absorbed) in the form of electromagnetic radiation. The energy E of a radiation is given by
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 E= hν
where h is the Planck's constant = 6.626×10-34Js and ν is the frequency (number of waves that
pass through a particular point in one second).
Evidently the energy is always emitted in multiple of hν, like hν, 2hν, 3hν, but never1.5hν.

The energy of an electron in such stationary nth orbit is

En =
which is equal to 13.6×1.6×10-19 Joule =13.6 ev for H-atom in the ground state.

3) Only those orbits are allowed for which the angular momentum of the electron is an
𝒉
integral multiple of .
𝟐𝝅
𝒉
Thus, 𝒎𝒗𝒓 = 𝒏 where n=1, 2, 3, 4 etc positive integers.
𝟐𝝅

Spectra of hydrogen atom given by Balmar’s experimental formula obtained from

experimental data further modified by Rydberg and Ritz:
 = = 𝑅𝑍  − 


where n2> n1, R is the Rydberg’s constant=1.0973731x107 m-1

n1=1 and n2=2, 3, 4, 5…. Lymann series, UV region

n1=2 and n2=3, 4, 5, 6…. Balmar series, visible region

n1=3 and n2=4, 5, 6, 7….Paschen series, IR region

n1=4 and n2= 5, 6, 7, 8….Bracket series, IR region

n1=5 and n2=6, 7, 8, 9, …Pfund series, IR region

Importance of Bohr’s theory:

1. Bohr’s model was a conceptual breakthrough in classical physics. He first introduced the idea
of quantized energy levels which was later confirmed by wave mechanics.

2. Bohr’s shell was very useful to describe the X-ray spectra of heavy elements.

3. It facilitates to obtain the electronic structure of element.

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Limitations

1. Even for simple H-atom the details of the structures in the spectra could not be explained by
Bohr’s circular orbits and Sommerfield found it necessary to postulate elliptical orbit giving rise
to a second quantum number called azimuthal quantum number ‘l’ and also to consider the
relativistic mass change of the revolving electron. Although the use of relativistic elliptical orbit
help to explain the fine structure of one electron atom or ions, serious discrepancies between
theory and experiment appeared for multi electron atoms.

2. Bohr’s theory could not account for the relative intensity and polarization of the different
spectral lines. But he had to put forward correspondence principle to explain intensity.

3. The Bohr’s theory was incomplete and failed to explain the splitting of spectral lines in
magnetic field called Zeeman’s effect. This effect was explained by introduction of third
quantum number called magnetic quantum number ‘m’ .The new quantum number was related to
the orientation of elliptical orbit in space and introduced three dimensional or spacial
quantization.

4. Additional difficulties appeared in connection to appearance of multiple structure of certain

elements which are quite widely separated relative to fine structural lines explained by
Sommerfield. The well known Na-line of 5895.93Ǻ and 5889.96 Ǻ are example of a doublet.
This require the introduction of a forth quantum number called spin quantum number‘s’.

5. According to Heisenberg’s uncertainty principle, the position as well velocity of a moving

electron cannot be measure accurately at one time. So the Bohr’s concept of stationary orbit
where electron moves with constant speed at a fixed radius around the nucleus is practically not
possible.

Wave particle duality

From Bohr’s model the question arose that why an electron is restricted to orbiting the nucleus at
fixed distance? Bohr could not provide any logical answer. In 1924 Louis de Broglie provided an
answer to this question. Broglie measured that light waves can behave like a stream of particle
(photon), and then perhaps particles such as electron can posses’ wave properties. According to
him an electron bound to the nucleus behave like a standing or stationary wave (a wave which do
not travel). He considered that if an electron does behave like a standing wave in the hydrogen
atom, then the length of the wave must fit the circumference of the orbit exactly, otherwise the
wave would partially cancel itself on each successive orbit. The circumference of an allowed
orbit (2πr) and the wave length λ are related as:

2πr = n λ

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where r= radius of the orbit, n=1, 2, 3, ….Because n is an integer,

It follows that r can have only certain values as n increases from 1 to 2 to 3 and so on. Since the
energy of the electron depends on the size of the orbit (value of r) so its value must be quantized.
De Broglie thus concluded that waves can behave like particles and particles can exhibit wave
like properties. He deduced that the particle and wave properties are related as

𝒉
=
𝒎𝒗
(where λ, m and v are wavelength associated with a particle, its mass and velocity respectively).
The equation implies that a particle in motion can be treated as wave and wave can exhibit the
properties of a particle.

Now if a particle of mass m moving with a speed of light c, then from mass energy relation of
Einstein its energy E= mc2, and from Planck’s equation the photon energy E= hν,

So comparing E= mc2 and E= hν

Or mc2 = hν = hc/λ

Or mc = h/ λ

Or = = =

Significance of de Broglie’s equation: The de Broglie’s equation is applicable for all particles but
wave aspect is of significance only with tiny particle like electrons. Let us compare the de
Broglie’s wave length associated with:

a) Large mass: Suppose a cricket ball of mass 200 g (0.2 kg) is moving a speed of 100 m/s then
. × ˄
λ= = 3.3125×1035 m, which is too small to be measured and has no
. ×
significance.

b) Small mass: Let us consider an electron mass 9.11×10-31 kg moving with a speed of 6×106m/s
. × ˄
Then wavelength λ= =1.21 × 10-10 m,
. × ˄ × × ˄

which is measurable and of real significance. It means that de Broglie’s relation has no
significance in everyday life, since in everyday life we come across macroscopic objects.

We can derive Bohr’s quantization postulate from de Broglie’s equation, λ=h/mv, In order that
electron wave may be completely in phase, the circumference of circular orbit must be an
integral multiple of wavelength (λ) i.e;

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 𝒏 𝒉
2r = = 𝒏
 𝒎𝒗

𝒏𝒉
Or, mvr =
𝟐

i.e. Angular momentum of an electron revolving around the nucleus in circular orbits is an
integral multiple of h/2π. This is nothing but Bohr’s postulate.

Heisenberg Uncertainty Principle: Calculations on the Bohr’s model of an atom require precise
information about the position of an electron and its velocity. It is difficult to measure both
quantities accurately at the same time. An electron is too small to see and only be observed if
perturbed e.g.; we could hit the electron with another particle such as a photon or an electron, or
we could apply an electric or magnetic field to locate its position precisely but it will inevitably
change the momentum and direction. Heisenberg stated that the more precisely we can define the
position of an electron, less certainly we are able to define its momentum, and vice versa. If Δx is
the uncertainty in defining the position and Δp is the uncertainty in measuring momentum, then
the uncertainty principle may be expressed mathematically as:

Δx Δp where h is the Planck's constant=6.626×10-34Js.



Or, Δx mΔv where Δv is the uncertainty in measuring velocity



To measure the position of revolving electron we have to employ photons of light which strikes
the electron and the reflected photon is seen through a microscope. According to the principles of
optics, the accuracy of measurement of position of a particle depends on the wavelength (λ) of
the light used. In other words, uncertainty in position is ± λ. To decrease the uncertainty in
position, shorter wavelength radiation can be employed. But shorter wavelength or higher
frequency means higher energy and consequently this high energy photon on striking the moving
electron causes change in speed as well as direction of motion of electron so there will be greater

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uncertainty in momentum. Again if we use photons of higher wavelength or lower frequency
means lower energy there will be greater uncertainty in measuring position.

Significance of uncertainty principle: This principle is applicable only for microscopic particle
such as electron and has no significance in everyday life where we are come across with mostly
macroscopic objects, and hence we can find the position and velocities/momentum of moving
bodies of appreciable size accurately.

From Heisenberg’s uncertainty principle we can easily show mathematically that an electron
cannot exist in nucleus. If electron were to exist within the nucleus, then the uncertainty in its
position is given by radius of nucleus, r=10 -14 m.

Now, Δx mΔv


 Δv ≥
. .

. ˄
≥ ≥ 6×109m/s
. ˄ . ˄

This is much higher than velocity of light (3×108m/s). Hence electron cannot exist inside
nucleus.

Heisenberg’s uncertainty principle is not applicable for stationary electron as we can accurately
determine the position of a stationary electron using photon of shorter wavelength.

Three dimensional model of atom: To accept Heisenberg’s uncertainty principle the concept of
orbit (where the position and velocity of an electron must be known exactly) should be replaced
by probability of finding an electron in a particular position or volume in space (orbital). The
Schrodinger’s wave equation provides a satisfactory description of an atom. Solutions of the
wave equation are called wave functions , the probability of finding an electron at a particular

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point in space whose coordinates are x, y z is 2 (x, y, z) and the well known form of
Schrodinger’s wave equation is as follow:

   
2 + (E-V)  = 0, where 2= + + , E=total energy , V= Potential energy of the
  
system, m=mass of electron, h= Planck’ constant.

Acceptable solutions to the wave equation which are physically possible must have the following
properties:

1. Must be continuous
2.  must be finite
3.  must be single valued
4. The probability of finding the electron over all the space from +∞ to -∞ must be equal
to 1.

The probability of finding an electron at a particular point in space whose coordinates are x, y z
is 2, so

 dx dy dz = 1

Several wave functions 1, 2, 3… will satisfy these conditions to the wave equation, and each
of these has a corresponding energy E1, E2, E3… Each of these wave functions 1, 2, 3 etc. is
called orbital, by analogy with Bohr’s orbit. In a hydrogen atom, the single electron occupies
lowest of the energy levels E1, called the ground state and the corresponding wave function 1
describes the orbital, that is the volume in space where there is a high probability of finding the
electron. For a given type of atom, there are a number of solutions to the wave equation which
are acceptable and each orbital may be described uniquely by a set of three quantum numbers, n,
l and m (principal, subsidiary and magnetic). The subsidiary quantum number l describes the
shape of the orbital and it has value 0, 1, 2, 3…., (n-1). When l=0, the orbital is spherical called s
orbital; l=1, the orbital is dumb-bell shaped and called p orbital; when l=2, the orbital is double
dumb-bell shaped and called d orbital and when l=3 a more complicated f orbital is formed (see
figure).The letters s, p, d and f come from the spectroscopic terms sharp, principal, diffuse and
fundamental, which were used to describe the lines in the atomic spectra. Examination of a list of
all the allowed solutions to the wave equation shows that the orbitals fall in two groups.

In the first group of solutions the value of  and hence the probability of finding the electron 2,
depends only on the distance r from the nucleus, and is the same in all directions.=f(r), this
leads to a spherical s orbital whose subsidiary quantum number l=0 and also magnetic quantum
number m=0, so there is one such orbital for each value of n.

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In the second group of solutions the value of  depends on the distance r from the nucleus and
on the direction in space (x, y, z). Orbitals of this kind occur when the subsidiary quantum
number l=1. These are called p orbitals and there are three possible values of the magnetic
quantum number (m=-1, 0 and +1). These are three orbitals which are identical in energy, shape
and size; differ only in direction in space. These three solutions in the wave equation may be
written

x=f(r) f(x)

y=f(r) f(y)

z=f(r) f(z)

Orbitals that are identical in energy are termed degenerate, and thus three degenerate p orbitals
occur for each of the values of n=2, 3, 4…

The third group of solutions to the wave equation depends on the distance r from the nucleus and
also on two directions in space e.g.;  =f(r) f(x) f(y), this group of orbitals has l=2 and these are
called d orbitals. There are five solutions corresponding to m=-2, -1, 0, +1, +2, which are all
equal in energy. The five degenerate d orbitals occur for each of the values of n=3, 4, 5…

A further set of solutions occurs when l=3, and these are called f orbitals. There are seven values
of m=-3, -2, -1, 0, +1, +2, +3 and seven degenerate f orbitals are formed when n=4, 5, 6….

Atomic orbital

Principle Quantum Subsidiary Quantum Magnetic Quantum Symbol

number number number
n l m s
1 0 0 1s
2 0 0 2s
2 1 -1, 0, +1 2py, 2pz, 2px
3 0 0 3s
3 1 -1, 0, +1 3py, 3pz, 3px
3 2 -2, -1, 0, +1, +2 3dxy, 3dyz, 3dz2, 3dxz,
3dx2-y2
4 0 0 4s
4 1 -1, 0, +1 4py, 4pz, 4px
4 2 -2, -1, 0, +1, +2 4dxy, 4dyz, 4dz2, 4dxz,
4dx2-y2
4 3 -3, -2, -1, 0, +1, +2, 4fx(x2-3y2), 4fy(x2-z2), 4fxz2,
+3 4fz3, 4fyz2, 4fxyz, 4fy(3x2-y2)

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Three quantum numbers n, l and m are needed to define an orbital. Each orbital can hold up to
two electrons, provided they have opposite spins. Thus a fourth quantum number called spin
quantum number s is needed to define the spin of electron in an atom.

Pauli Exclusion Principle: No two electrons in one atom can have their four quantum numbers
the same.

Hund’s rule: Electrons will fill all the degenerate orbitals with parallel spins first before pairing
up in one orbital.

Aufbau’s Principle: Aufbau (German aufbauen, “to build up”) principle tells us that electrons
fill the orbitals in the order of increasing their energy level.

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Particle in a 1-dimensional box: A particle in a 1-dimensional box is a fundamental quantum
mechanical approximation describing the translational motion of a single particle confined inside
an infinitely deep well from which it cannot escape. The solutions to the problem give possible
values of E and ψ that the particle can possess. E represents allowed energy values and ψ(x) is a
wave function, which when squared gives us the probability of locating the particle at a certain
position within the box at a given energy level. The potential energy is 0 inside the box (V=0 for
0<x<L) and goes to infinity at the walls of the box (V=∞ for x<0 or x>L). We assume the walls
have infinite potential energy to ensure that the particle has zero probability of being at the walls
or outside the box. Doing so significantly simplifies our later mathematical calculations as we
employ these boundary conditions when solving the Schrödinger Equation.

A particle in a 1D infinite potential well of dimension L

The time-independent Schrödinger equation for a particle of mass m moving in one direction
with energy E is

ℏ  ( )
− +V(x)ψ(x)=Eψ(x)


Where ℏ is the reduced Planck Constant where ℏ=h2π, m is the mass of the particle, ψ(x) is the
stationary time-independent wave function, V(x) is the potential energy as a function of position,
E is the energy, a real number. This equation has been well studied and gives a general solution
of:

√ 
ψ(x)=Asin(kx)+Bcos(kx), where A, B, and k are constants. And k= √

The solution to the Schrödinger equation we found above is the general solution for a 1-
dimensional system. We now need to apply our boundary conditions to find the solution to our
particular system. According to our boundary conditions, the probability of finding the particle at

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x=0 or x=L is zero. When x=0, sin(0)=0 and cos(0)=1 therefore, B must equal 0 to fulfill this
boundary condition giving:

ψ(x)=Bsin(kx)

Now applying x=L and ψ(L)=0

0 = Bsin(kL), either B=0 or the sin term is 0, now B cannot be 0 it’s a constant so

Or sin(kL)=0=sin(n)

Or kL= n

√ 
Or √
L= n

Or E =

Where n = 1, 2, 3…

This is an important result that tells us the energy of a particle is quantized and the lowest
possible energy of a particle is NOT zero. This is called the zero-point energy and means the
particle can never be at rest because it always has some kinetic energy.

This is also consistent with the Heisenberg Uncertainty Principle: if the particle had zero energy,
we would know where it was in both space and time.

The wave function ψ and probability ψ 2 of finding for a particle in a box at the n=1and n=2
energy levels look like this:

Notice that the number of nodes (places where the particle has zero probability of being located)
increases with increasing energy n. Also note that as the energy of the particle becomes greater,
the quantum mechanical model break down as the energy levels get closer together and overlap,
forming a continuum. This continuum means the particle is free and can have any energy value.
At such high energies, the classical mechanical model is applied as the particle behaves more
like a continuous wave. Therefore, the particle in a box problem is an example of Wave-Particle
Duality.

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 Atomic Structure Question
1. Write the wave function and the total energy of particle in a one-dimensional box for n=2 state. Indicate the
number of nodes in the wave.
2. Calculate the wavelength of spectral lines when an electron drops from the third to the second Bohr orbit in a
hydrogen atom. (R=1.09678×105 cm-1). In which region of electromagnetic spectrum does this radiation fall?
3. What is de Broglie hypothesis? Consider a beam of electron with a speed of 5.31x106 m/s and calculate the de
Broglie wavelength (Mass of electron = 9.11 x 10-31 kg)
4. Calculate the wavelength of emitted light for the transition of energy level n=4 to energy level n=1 for the
hydrogen electron transition. In which region of electromagnetic spectrum does this radiation fall?
(RH=1.096776x107m-1)
5. Consider a beam of electron with a speed of 5.31x106 m/s and calculate the de Broglie wavelength (Mass of
electron = 9.11 x 10-31 kg; h=6.626×10−34Js).
6. Write the total energy of a particle in a one dimensional box for ground state.
7. The probability of finding an electron in a stationary orbit around nucleus must be
(a) Zero (b) unity (c) infinity (d) double
8. State Pauli’s exclusion principle.
9. Write the possible values of m for an electron with l=2.
10. State and explain de Broglie’s principle for the wave particle duality.
11. Define Heisenberg’s uncertainty principle.
12. What are the significances of the four quantum numbers?
13. What is the importance of de Broglie’s relation?
14. In what way Heisenberg’s uncertainty principle contradicts the concepts of Bohr’s stationary orbit for electrons.
15. What is the designation of orbital having n=4 and l=3?
16. Which quantum number specifies the shape of orbital?
17. What is  ? What information is conveyed by  and 2?
18. Calculate the energy per photon for radiation of wavelength 650pm.
Answer. E=hυ=hc/λ=(6.625x10-27 Js x 3x108ms-1)/650x10-12m=3058 x 10-16 J
19. Kinetic energy of a subatomic particle is 5.85x10-25 J. Calculate the frequency of the particle wave. (Given
Plank’s constant, h= 6.6x10-34kg m2s-1).
Answer. K.E. =1/2 mv2= 5.85x10-25 J= 5.85x10-25 kg m2s-1
Also wavelength λ= h/mv=v/υ
Or υ=mx2/h= 2KE/h= 2x5.85x10-25 kg m2s-1/6.6x10-34kg m2s-1=1.773x109s-1
20. Calculate the uncertainty in velocity of a cricket ball (mass=0.1kg), if the uncertainty in its position is of the
order of 100 pm.
Answer. M=0.1kg, Δx=100pm=10-10m
Now Δx. m Δv≥h\4π
Δv≥ 6.6x10-34kg m2s-1/(4x3.14x0.1kgx10-10m) ≥ 5.25x10-24ms-1
21. The uncertainty in the position and velocity of a particle are 10-10m and 5.27x10-24 ms-1 respectively. Calculate
the mass of the particle. Answer. 100g.
22. State and explain Pauli Exclusion Principle.

23. Write down the Schrodinger wave equation mentioning the terms involved in the equation.

24. Write down the possible values of four quantum numbers for the valence electrons of calcium (Ca-20).

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