Atomic Structure

Mrinal Kanti Roy

Lecturer (Chemistry)
Mymensingh Engineering College
 Rutherford's atomic model
(1)An atom consists of a small nucleus containing all positive
charges of the atom and practically the whole of its mass
(2) The nucleus is surrounded by a number of electrons equal to
the number of positive charges on the nucleus.
(3) The electrons are in constant motion round the nucleus like
that of planets round the sun in such a way that the electroststic
force of attraction between the electrons and positive nucleus is
counterbalanced by the centrifugal force.
Limitations:
1) Rutherford’s model could not explain the stability of atom. According
to electromagnetic theory, the charged particle under acceleration should
continuously emit radiation. Hence the electron moving in the orbits must
lose energy and fall into the nucleus. But this is not happening.
2) This model could not explain the electronic structure and energy of
electrons.
3) It could not explain the atomic spectra.
 Bohr’s Model
In 1913, Niels Bohr (1885-1962) proposed another model of the atom where
electrons move around the nucleus in circular paths. Bohr’s atomic model is built
upon a set of postulates, which are as follows :
1. The electrons move in a definite circular paths around the nucleus . He called
these circular paths as orbits and postulated that as long as the electron is in a given
orbit its energy does not change (or energy remains fixed). These orbits were
therefore referred to as stationary orbits or stationary states or non radiating orbits.
2. The electron can change its orbit by absorbing or releasing energy. An electron at
a lower (initial) state of energy, Ei can go to a (final) higher state of energy, Ef by
absorbing a single photon of energy given by
E = hv = Ef – Ei
Similarly, when electron changes its orbit from a higher initial state of energy Ei to
a lower final state of energy Ef , a single photon of energy hν is released.
3. The angular momentum of an electron of mass me moving in a circular
orbit of radius r and velocity v is an integral multiple of h/2.
mvr = nh/2
where n is a positive integer, known as the principal quantum number.
Limitations:
(1) Bohr’s model of an atom failed to explain the Zeeman Effect (effect
of magnetic field on the spectra of atoms).
(2) It also failed to explain the Stark effect (effect of electric field on the
spectra of atoms).
(3) It could not explain the spectra obtained from larger atoms.
Calculation of radius of orbits:
Consider an electron of charge e revolving around a nucleus of charge Ze, where Z
is the atomic number and e the charge on a proton. Let m be the mass of the
electron, r the radius of the orbit and ν the tangential velocity of the revolving
[Link] electrostatic force of attraction between the nucleus and the electron
(Coulomb’s law),
Consider an electron of charge ‘e’ revolving around a nucleus of charge ‘ze’, where ‘z’
is the atomic number and ‘e’ the charge on a proton. Let ‘m’ be the mass of the
electron, ‘r’ be the radius of the orbit and ‘v’ the tangential velocity of the revolving
electron.
The electrostatic force of attraction between the nucleus and the electron (coulomb’s
law) = ze × e / r2 .
The centrifugal force acting on the electron = mv2 / r
Bohr assumed that these two opposing forces must be balancing each other exactly to
keep the electron in orbit. Thus,
Ze2/ r2 = mv2/r
For hydrogen z = 1, therefore,
e2/ r2 = mv2/r -------(1)
Multiplying both sides by ‘r’
e2/r = mv2 -------(2)
According to one of the postulates of the Bohr’s theory, angular momentum of the revolving
electron is integral multiple of h/2π.
mvr = nh/2π
or, v = nh/2πmr-----------(3)
Substituting the value of ‘v’ in equation (2),
e2/r = m( nh/2πmr)2
So, r = n2h2/4π2me2 -------(4)
Since the value of h, m and e had been determined experimentally, substituting these values in
(4), we have r = n2 × 0.529 × 10–8 cm ...(5)
where n is the principal quantum number and hence the number of the [Link] n = 1, the
equation (5) becomes
r = 0.529 × 10–8 cm = α0 ...(6)
This last quantity, α0 called the first Bohr radius was taken by Bohr to be the radius of the
hydrogen atom in the ground state. This value is reasonably consistent with other information on
thesize of atoms. When n = 2, 3, 4 etc., the value of the second and third orbits of hydrogen
comprising the electron in the excited state can be calculated.
Energy of electron in each orbit:
For hydrogen atom, the energy of the revolving electron, E is the sum of its kinetic
energy (1/2 mv2) and potential energy (- e2/r)
E= 1/2 mv2 - e2/r...............(7)
From equation (1)
mv2/r = e2/r
Substituting the value of mv2 in (7)
E=1/2×e2/r - e2/r
or,E = -e2/2r ...................(8)
ubstituting the value of r from equation (4) in (8)
E= -e2/2× 4π2m2/n2h2
=-2π2me4/n2h2
Substituting the value of r from equation (4) in (8)
E= -e2/2× 4π2m2/n2h2
=-2π2me4/n2h2
Explanation of Line Spectrum of Hydrogen Atom
When a high potential is applied to hydrogen gas at low pressure
in a discharge tube, it starts emitting a bright light. It is separated
into several radiations and forms a spectrum upon passing
through a prism or grating. The spectrum consists of separate
lines corresponding to different wavelengths. This is called
Hydrogen atomic spectrum. The spectral lines are formed due to
electronic transitions from one energy level to another. These
lines are divided into five series according to the range of
wavelengths as follows.
Spectral series Spectral region n1 n2
1. Lyman series Ultra-violet 1 2,3,4,5,6,7,_ _ _ _
2. Balmer series Visible 2 3,4,5,6,7,_ _ _ _
3. Paschen series near infra-red 3 4,5,6,7,_ _ _ _
4. Brackett series infra-red 4 5,6,7,_ _ _ _
5. Pfund series far infra-red 5 6,7,_ _ _ _
The wave numbers of spectral lines in each series can be
calculated using Rydberg's equation as follows

Where n1 and n2 are the principal quantum numbers of orbits

corresponding to the electronic transition. RH = Rydberg's
constant = 1,09,677 cm-1 ,Z = atomic number.
Electronic structure of Atom
The new quantum mechanics, which takes into account the particulate and wave
nature of matter, is termed the Wave mechanics.
de Broglie’s Equation
de Broglie had arrived at his hypothesis with the help of Planck’s Quantum Theory
and Einstein’s Theory of Relativity. He derived a relationship between the
magnitude of the wavelength associated with the mass ‘m’ of a moving body and its
velocity. According to Planck, the photon energy ‘E’ is given by the equation
E = hν ...(i)
where h is Planck’s constant and v the frequency of radiation. By applying
Einstein’s mass-energy relationship, the energy associated with photon of mass ‘m’
is given as
E = mc2 ...(ii)
where c is the velocity of radiation
Comparing equations (i) and (ii)
mc2 = hν = h c/λ (∵ v=c/λ)
or, mc = h/λ .......(iii)
mass × velocity = h/wavelength
or, momentum (p) = h/wavelength
or, momentum ∝ 1/wavelength
The equation (iii) is called de Broglie’s equation and may be put in words as : The
momentumof a particle in motion is inversely proportional to wavelength, Planck’s
constant ‘h’ being the constant of proportionality.
 Dual Nature of Electrons
French physicist named Louis de-Broglie in 1924 said electrons have dual nature,
as both particle and wave nature can be seen in an electron.
It stated that when small particles like electrons can pass wave nature when they
are in motion, it was a new theory.
Now, de-Broglie introduced the wavelength
λ=h/mv………..(1)
Where, m is mass of particle, vis velocity and h is planck's constant.
Derivation of de-Broglie’s equation:
According to planck's equation
E=hf=hc/λ−(2)
Where, Eis energy, f is frequency and c is speed of light.
Now, according to Einstein’s mass energy relationship
hc/λ=mc2
or,hc=mc2λ
Change the above equation with respect to λ
λ=hc/mc2
Cancel c from numerator and denominator
λ=h/mc−(4)
This is the same as de-Broglie’s equation.
Also, Davison and Germer, by performing diffraction effects on an electron beam,
verified the dual nature of the electron. Consider an electron accelerated at
potential V, than its kinetic energy is
1/2(mv2)=eV
or,mV2=2eV
or,mV=2e
Now, by multiplying mV on both the sides
(mV)2=2eVm
taking√ on both the sides
mV=√2eVm −(5)
Substituting equation (5) and (1) we get
λ=h/√2eVm−(6)
Now, Bohr’s theory can also be related to de-Broglie’s equation, therefore wavelength of an
electron is calculated by Bohr’s orbit and can be related to its circumference that is 2πr, and
by multiplying with a whole number n.
2πr = nλ
Now, from de-Broglie’s equation, by applying
2πr = nh/mV
Then, h/mV=2πr/n
Now, by interchanging quantity we get
mVr = nh/2π−(7)
Which is considered as Bohr’s equation.
Now, de-Broglie is not significant in daily life because it is considered for micro-particle
and not on macro-particle.
[Dual nature of electrons can be related to dual nature of light. Light behaves as both
particles and waves. It acts as an electromagnetic wave when in transmission in space,
and interacting with electrons acts as if a particle i.e. photon.]
 Photoelectric Effect
When a beam of light of sufficiently high frequency is allowed to strike a metal
surface invacuum, electrons are ejected from the metal surface. This phenomenon is
known as Photoelectric effect and the ejected electrons Photoelectrons. For
example, when ultraviolet light shines on Cs(or Li, Na, K, Rb) as in the apparatus
shown in Fig , the photoelectric effect occurs.
With the help of this photoelectric apparatus the following observations can be
made :
(1) An increase in the intensity of incident light does not increase the energy of the
photoelectrons.
(2) The kinetic energy of the photoelectrons increases linearly with the frequency
of theincident light.
 Quantum number
Quantum numbers are used to describe the position and energy
of an electron in an atom. There are four types of quantum
numbers.
i) Principal quantum number
ii) Azimuthal quantum number
iii) Magnetic quantum number
iv) Spin quantum number
 Principal quantum number
1. Principal quantum number was proposed by Bohr to explain the
hydrogen atomic spectrum.
2. It denotes the main energy level (or shell or orbit).
3. It is denoted by 'n'. It can have positive integral values from 1,2,3,4,_
_ _ (or K,L,M,N_ _ _ ).
4. It also describes the energy and size of the orbit. The energy and the
size of orbit increases with increase in 'n' value.
5. The maximum number of electrons that can be accommodated in a
given shell is equal to 2n2.
 Azimuthal quantum number
1. Azimuthal quantum number was proposed by Sommerfield in order to explain
the fine hydrogen atomic spectrum.
2. It denotes the sub-levels (or sub-shells) in the atom. It is denoted by 'l'
3. The number of sub-levels in a given main energy level is equal to the principal
quantum number 'n'. These sub-levels are indicated by azimuthal quantum number
'l' which can have values from 0 to n-1. For ex: In an orbit of principal quantum
number n=3, there are three sublevels denoted by l =0,1 and 2.
4. Azimuthal quantum number also describes the angular momentum of electron
and shape of orbitals present in that sublevel.
E.g.l = 0 (s)--- spherical
l = 1 (p)--- dumbbell
l = 2 (d)--- double dumbbell
 Magnetic quantum number
1. Magnetic quantum number was proposed by Lande in order to explain
the Zeeman and Stark effects. The splitting of spectral lines in strong
magnetic field is called Zeeman effect and splitting in strong electric
field is called Stark effect.
2. It is denoted by 'm'. It describes the orientation of orbitals.
3. The number of orientations possible for orbitals in a given sublevel 'l'
is equal to the (2l+1) and can have values from -l_ _ _ 0 _ _ _+l.
E.g. The number of orientations (m values) possible for a sublevel l=2 is
(2 x 2)+1 = 5 and the values of m = -2,-1,0,+1 and +2.
 Spin quantum number
1. It was proposed by Goudsmit and Uhlenbeck to explain the double
line structure of alkali metal spectra.
2. Spin quantum number denotes the spin of the electron on its own axis.
It is denoted by 's'. It can have only two values(+½ and -½).
3. The clockwise spin is indicated by +½ or upwards arrow(↑) and anti-
clockwise spin by -½ or downwards arrow(↓)
 Aufbau ( or building up) Principle
This principle is concerned with the energy of the atom and states that the
electrons should occupy. The electrons occupy the orbitals in such a way
that the energy of atom is minimum. In other words the electrons in an
atom are filled in the increasing order of their energies
i.e. the orbital with the lowest energy is filled up first while that with the
highest energy is filled up in the end.
The order of orbital energies can be determined by the following (n + l)
rules
Rule 1: An orbital with a lower value for (n + l) has lower energy. For
example, the 4s orbital (n + l = 4+0=4) will fill before a 3d orbital (n + l
= 3 + 2 =5).
Rule 2: If the value of (n + l) is same for two orbitals then the orbital
with lower value of n will be filled first. For example, the 3d orbital (n +
l = 3+2=5) will fill before a 4p orbital (n + l = 4 + 1 =5). Following these
rules the increasing order of the orbital energies comes out to be
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
 Pauli’s Exclusion Principle
This principle concerns the spin of electrons present in an orbital.
According to the Pauli’s principle, no two electrons can have all the
four quantum numbers to be same.
For example, if a given electron in an atom has the set of four quantum
numbers as n =2, l=1, ml=1 and ms= + ½ then no other electron in the
atom can have the same set of quantum numbers.
 Hund’s Rule
Every orbital in a subshell is singly occupired with one electron before any one
orbital is doubly occupied,and all electrons in singly occupied orbitals have the
same [Link] example, the six electrons in carbon distribute as
1s2 2s2 2px1 2py12pz0
 Heisenberg uncertainty principle
An important consequence of the wave-particle duality of matter and
radiation was discovered by Werner Heisenberg in 1927 and is called the
uncertainty principle.
According to this principle it is not possible to simultaneously measure
both the position and momentum (or velocity) of an electron
accurately. In simple words we may state that more accurately you
measure a particle’s position, the less accurately you’re able to measure
its momentum, and vice versa. Mathematically, the Heisenberg principle
can be expressed in terms of an inequality

Δx Δp ≥ h/4π
Where Δx and Δp are the uncertainities in the measurements of position
and momentum respectively. If the position of an object is known exactly
(i.e., Δx = 0), then the uncertainty in the momentum must be infinite,
meaning that we cannot say anything about the velocity. Similarly, if the
velocity is known exactly, then the position would be entirely uncertain
and the particle could be anywhere. It means that we cannot say anything
about the position of the particle. In actual practice none of the two
properties can be measured with certainty. Due to the small value of the
Planck’s constant , h ( 6.626 x 10-34 J s) this principle is not relevant
while making measurements of large objects like car, bus or aeroplane
etc.
It is relevant, only when you are making measurements on very
small objects such as electrons. Heisenberg’s principle
questioned the validity of Bohr’s model. It is so because
according to Bohr’s model we can precisely calculate the radius
of the orbit ( i.e., the position of the electron) and the velocity of
electron in it. But it is not possible according to Heisenberg’s
principle. It motivated many scientists to develop newer models
of the atom using the dual nature of the electron.
 Schrödinger’s Wave Equation
In order to provide sense and meaning to the probability approach, Schrödinger
derived an equation known after his name as Schrödinger’s Wave Equation.
Calculation of the probability of finding the electron at various points in an atom
was the main problem before Schrödinger. Hisequation is the keynote of wave
mechanics and is based upon the idea of the electron as ‘standing wave’ around
the nucleus.