Atomic Structure

Atomic structure: Overview of Bohr’s atomic model,

Schrodinger wave equation, Interpretation of wave
function (radial and angular), Hydrogen like atom,
Concept of atomic orbitals.

Books:
1. Atkins’ Physical Chemistry by Peter Atkins and Julio de Paula
2. Inorganic Chemistry by Gary L. Miessler and Donald A. Tarr
 Atoms
• Two regions.
• Nucleus- protons and neutrons. (Occupies very
small space)
• Electron cloud- region where you might find
an electron. [Occupies large (most of the)
space]

Subatomic particles

Name Symbol Discovered by, year

Electron e- J. J. Thomson, 1897

Nucleus n+ p E. Rutherford, 1911

Proton p+ H.G.J. Moseley, 1913

 Atomic Structure

Bohr’s Model (planetary Schrödinger Model (electron

model)-1914 cloud model)- 1926
Assumes electron as particle Assumes electron as wave

Got Nobel Prize in 1922 for Got Nobel Prize in 1933

foundational contribution to for his Schrödinger wave
understand atomic structure. equation for H-like atoms.
 Bohr’s Model ∞ 0.00 eV

5 −0.54 eV
4 −0.85 eV
3 −1.51 eV
r = εon2h2/πμe2Z
2 −3.4 eV

Increasing energy
E = −Z2e4μ/8εₒ2n2h2
Or, E = −13.6/n2 eV

E = −Ze2/8πεₒr
1 −13.6 eV

μ = reduced mass of electron-nucleus

combination
Z = Charge of nucleus or atomic number
e = electronic charge
h = Planck’s constant
n = principal quantum number
 Drawbacks of Bohr model
 The model only worked for hydrogen-like atoms.
 Could not explain why the intensity of the spectra lines were
NOT all equal.
 The existence of fine and hyperfine structure in spectral lines.
 The Zeeman effect - changes in spectral lines due to external
magnetic fields.
Wave nature of electron was not considered in Bohr’s model

Information gained from Bohr’s model

It provide foundation to understand atomic structure.

The total energy of electron in H-atom it predicts is exactly agree with

these obtained from Schrodinger equation (discussed later).
 Photoelectric Effect (1905)
Quantum revolution
A beam of light is not a wave
propagating through space, but
rather a collection of discrete
wave packets (photons), each
with energy h

Emission of electrons from metals when exposed to

(ultraviolet) radiation proves particle nature of electron.
 Photoelectric Effect
The kinetic energy of the emitted electron Ek = h   = h(  0)
 is the frequency of incident radiation
 is the work function (minimum energy required to remove an electron from the
metal surface )
 = h0 , 0 is the threshold frequency and for radiation with  > 0, electron emitted.
 de Broglie equation (1924)
(Wave-particle duality)

All the moving particles have wave properties. So electrons

have dual character.

The wave length of a particle moving with a velocity ‘v’ is

given by:

λ = h/mv

The wave length of a macroscopic object is insignificant to measure.

However, for an electron, the wave length is measurable.
Experimental proof of de Broglie hypothesis
Davisson–Germer experiment (1923-1927) confirms the de Broglie
hypothesis (wave-particle duality).

They discovered the wave nature of electron by getting a diffraction

pattern from a Ni crystal by bombarding a beam of electron.
Heisenberg’s uncertainty principle (1927)

The more precisely we can define the position of an electron

the less certainly we are able to define its velocity, and vice
versa.

Δx . ΔPx ≥ h/4π
 Heisenberg’s uncertainty principle
(Concept of orbital)
 The energy of spectral line is
measured with great accuracy, and
hence the energy of electron.
 Precision in energy  Precision in
momentum IR

 So there is large uncertainty in the Visible

location of electron.
 Hence orbits are replaced by orbitals
(the probability of finding an electron UV
in a given space).
 Orbitals are described by wave
functions.
 Schrödinger's equation
The Schrödinger equation describes the wave properties of an
electron in terms of position, mass, total and potential energy.

The simplest form of Schrodinger equation:

H=E
H = Hamilton operator
E = Total energy of electron
 = wave function of electron

H = −h2/8π2m 2 + V
V = potential energy, (V = − Ze2/4πor)

[−h2/8π2m 2 +V]  = E 
 Wave function () (PSI)

1. A wavefunction is a mathematical function (like sinx, ex).

Like any mathematical function it can have large value at
some place, small in other and zero elsewhere.
It can be real or complex

2. A wavefunction contains all information about the system

4. If the wavefunction is large at a point in space, the particle

has a large probability at that point

5. The more rapidly a wavefunction changes from place to

place, higher the K.E. of the particle it describes
 Wave function () (PSI)
How to determine the observables from wavefunction ()

By performing a set of well defined mathematically operations

on . These mathematical operations are called operators

(operator) (function)= (constant factor) (same function)

d ax
dx
   
e ae ax

(operator) (function)= (eigenvalue) (eigenfunction)

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 Understanding the Schrödinger equation

(Hamiltonian operator) (Eigenfunction) = (Eigenvalue) (Eigenfunction)

H=E
 Eigenfunction is the wave function of an electron corresponding to
the energy E.

 Eigenfunction is different for each eigenvalue.

 By solving Schrödinger equation one can find the wave functions

(eigenfuncctions) and the corresponding allowed energies
(eigenvalues).
(operator corresponding to an observable) () = (value of observable) ()
Hamiltonian operator is used to find out the total energy
 Understanding the Schrödinger equation

How to extract the information about the location of electron

from the wave function ?

The probability of finding the particle in an infinitesimal

volume, dV, about a given point is proportional to 2 dV.

Normalization
the probability of existence of the particle in
the entire space should be 1.



dx  1
 Identifying an eigenfunction
Q1. Show that eax is an eigenfunction of the operator d/dx,
and find the corresponding eigenvalue.

Q2. Show that eax² is not an eigenfunction of d/dx.

d/dx(eax²) = 2ax (eax²)

This is not an eigenvalue eventhough the same function occurs

on the right, because the function is now multiplied by a
variable factor (2ax), not a constant factor.
 Solutions of Schrödinger equation
[−h2/8π2m 2 +V]  = E 
There are many solutions to the above equation. However, the
acceptable solutions must satisfy following conditions.
1.  must be single valued.
2.  must be continuous.
3.  must be finite.
 For an atom several wave functions (1, 2, 3) will satisfy
these conditions and each of these has a corresponding energy
(E1, E2, E3)

 These wave functions are called as orbitals analogy to orbits in

Bohr’s theory.

 Each orbital is described uniquely by a set of three quantum

numbers, n, l, ml.
 Quantum Numbers
There are four quantum numbers.

Orbital is defined by three quantum numbers (n, l, ml).

An electron is defined by four quantum numbers (n, l, ml, ms).

Principal quantum number (n):

Determines the total energy of an electron.
E = −1/n2 (Z2e4μ/8εₒ2h2)
Or, E = 1/n2 (−13.6) eV
Has value 1, 2, 3, …………∞
 Quantum Numbers

Magnetic quantum number (ml):

Describe orientation of orbital in space.
It is the z-component of angular momentum.
(so it never be larger than the ‘l’ value)
It may have +ve z-component or
–ve z-component
So the value ranges from –l, ……0, …….+l
 Quantum Numbers

Spin quantum number (ms):

Describes orientation of electron spin in a magnetic field.

The value of ms either +1/2 (in the direction of the field)

or −1/2 (opposed to it).

Arises due to spinning of electron.

Radial and Angular part of wave function 

In 3D,  may be expressed either in Cartesian coordinates

(x,y,z) or in spherical coordinates (r,θ,ϕ).

r = represents the distance from the nucleus.

θ = is the angle from z-axis, it varies from 0-π.
ϕ = is the angle from x-axis, it varies from 0-2π.

(x,y,z) can be converted to (r,θ,ϕ) using:

x = r sinθ cosϕ
y = r sinθ sinϕ
z = r cosθ
 Radial and Angular part of wave function 

 may be separated into radial component and two angular components.

(r,θ,ϕ) = R(r) (θ ) (ϕ)

Combining the two angular components

(r,θ,ϕ) = R(r) Y(θ,ϕ)

radial angular
function function
 Radial and Angular part of wave function 
The radial function, R(r) :

The radial function is determined by the quantum numbers n

and l.

The radial probability function, 4πr2R2, is derived from the

radial part of the wave function. It describes the probability
of finding the electron at a given distance from the nucleus.
 Radial and Angular part of wave function 

The angular functions, (θ ) (ϕ) :

The angular function is determined by the quantum numbers

l and ml.

The angular functions, (θ ) (ϕ), describes shape of the

orbitals and their orientation in space.
 Hydrogen atom

Hydrogen has special significance

•No approximation is required in solution of Schrödinger equation
•Can get expression for energy levels

For H atom the Schrödinger wave equation can be written as

Ĥψ=Eψ

(ħ2/2m 2 +Ze2/r ) ψ = E ψ
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 Solution of Schrödinger wave equation
for Hydrogen atom

Solution of the Schrödinger wave equation (shown in spherical

coordinate) may be described as a product of two functions.

ψn,l,ml(r,,) = Rn,l(r)Yl,ml(,)
where Rn,l(r) is called the radial part of ψ, and Yl,ml(,) its angular
part.

The wavefunction of the electron in the hydrogenic atom is called an

atomic orbital. An orbital is a one-electron wavefunction.
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Solution of the Schrödinger wave equation: Some examples

1s atomic orbital (n = 1, l = 0, ml = 0
3 1
 Z  2  2  1  2
 1s = 2  e  
 a0   4 

Radial part Z = effective nuclear charge Angular part

ao = Bohr radius
ρ = 2Z r/n ao
r = distance from the nucleus
n = principal quantum number

3 1
Z 2
  1  2
R n, l = 2  e 2
Y l, ml (,) =  
 a0   4 
 1s atomic orbital (n = 1, l = 0, ml = 0
For H atom Z = 1, so
3 1
1 2
  1  2
 1s = 2  e 2
 
 a0   4 

 Y is a constant and does not depend on 

and  , s-orbitals are spherically symmetrical.
2p atomic orbitals (n = 2, l = 1, ml = +1, 0, −1

3
1  Z  2  / 2  3  2  z 
1

 2pz =    e    
2 6  a0   4   r 

Radial part (R n, l) Angular part (Y l, ml (,))

Note: Z is the atomic number and z is the z-direction/component

In polar coordinate the above equation becomes

3
1  Z  2   / 2 3  2
1

 2pz =    e   cos (Since, z = r cosθ)

2 6  a0   4 
2p atomic orbitals (n = 2, l = 1, ml = +1, 0, −1

For H atom Z = 1, so
3
1  1  2   / 2 3  2
1

 2pz =    e   cos
2 6 0
a  4 

 The angular variation of wave function depend

on cos .
 The probability density is proportional to cos2.
 The probability density has maximum value
along an arbitary axis (z-axis) on either side of the
nucleus ( at = 0 and 180o)
 2p atomic orbitals
Similarly the wave functions (real part of wave functions) of other two
p-orbitals are given below:
3
1  1  2  / 2  3  2
1

 2px =    e   sin  cos (Since, x/r = sinθcos)

2 6  a0   4 
3
1  1  2   / 2 3  2
1

 2py =    e   sin  sin  (Since, y/r = sinθsin)

2 6 0
a  4 
3d atomic orbitals (n = 3, l = 2, ml = +2, +1, 0, −1, −2)
(dxy, dxz, dyz, dx²-y², dz²)

1
1  15  2
xy Similarly the dxz, dyz
 3dxy = R n, l  
4   r2
Y (θ, )
1
1  15  2
x2 y 2
 3dx²-y² = R n, l   Since the angular part contains
4   r2 two or more variables, so these
orbitals have shapes in two
1
axial directions or more.
1 5 2
2 z2 x2 y 2
 3dz² = R n, l  
4  r2
 Nodal surface(s) of atomic orbitals
node

Nodal surface is a surface with zero electron density.

Nodes appear naturally as a result of the wave nature of the

electron. At the nodal surface the wave function changes its sign.

At nodal surface,  = 0
either R(r) = 0
or Y(,) = 0

Angular node
Radial node
 Nodal surface(s) of atomic orbitals
If Y(,) = 0, angular nodes result. Angular nodes are
planar or conical.
Number of angular nodes = l
Orbital No. of angular nodes
s- orbital 0
p-orbital 1
d-orbital 2 Total number nodal surface = n −1
f-orbital 3

If R(r) = 0, radial nodes or spherical nodes result.

Number of radial nodes = n−l −1
Orbital Radial Orbital Radial Orbital Radial
nodes nodes nodes
1s 0 2p 0 3d 0
2s 1 3p 1 4d 1
3s 2 4p 2 5d 2
Q. Describe the nodal surfaces for a 3dxy orbital, whose angular wave
function is
1
1  15  2
xy xz -plane
Y = 4  
  r

Ans. In nodal surfaces, Y = 0

yz -plane

Y = 0, when either x = 0 or y = 0
So the nodal surfaces are x = 0 (yz plane) and y = 0 (xz plane)
 Sign of atomic orbital

Sign of lobes does not mean electronic charge.

It represents the phase/direction of wave function.

Atomic orbital along positive axial direction has a positive sign and
negative axial direction has a negative sign.
z
y
dxz + ve phase
− +
x
+ − − ve phase
 Sign of atomic orbital
The angular part of s-orbitals contain constant value, no variables. So there is no
change in sign.

The angular part of p-orbital contains either x or y or z. Since the x, y, or z direction

may be positive or negative, so the wave function along positive axis has a positive
sign and along negative axis has negative sign.

The angular part of dxy, dxz, dyz contain product of two component. So the product
of signs gives the sign of the lobe.
For dx²-y², the angular part contains x2−y2. so the wave function is positive along x-
direction (positive and negative) and negative along y direction.
For dz² , the angular function contains 2z2−x2−y2, so the wave function is positive
along z direction (both positive and negative) and negative in xy-plane.