CY 101- Chemistry

Atomic Structure

Dr. Priyabrat Dash

Email: dashp@nitrkl.ac.in
Office: BM-406, Mob: 8895121141
Webpage: http://homepage.usask.ca/~prd822/
Dr. Priyabrat Dash
Email: dashp@nitrkl.ac.in
Office: BM-406, Mob: 8895121141
Webpage: http://homepage.usask.ca/~prd822/
Dr. Priyabrat Dash
Email: dashp@nitrkl.ac.in
Office: BM-406, Mob: 8895121141
Webpage: http://homepage.usask.ca/~prd822/
 Hydrogen atom
Hydrogen has special significance
•No approximation is required in solution of Schroedinger equation
•Can get expression for energy levels
•Spectral frequencies can be deduced

Since MN>>Me, the nucleus can be considered to be at rest

For H atom the Schrödinger wave equation can be written as

Ĥψ=Eψ
[- (h2/2m){2x2 +2y2 +2z2} +V] =E
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The potential, V between two charges is best described
by a Coulomb term,

V= - q1q2/ r

(ħ2/2m 2 +Ze2/r ) ψ = E ψ

It is convenient to describe the solutions to the Schrödinger

equation in spherical polar coordinates (r, ,) rather than
cartesian (x,y,z)

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 The Schrödinger equation in spherical polar coordinate is

h2  1   2   1     1  2  e2
  2 r  2  Sin  2 2 2
   E
2me  r r  r  r Sin     r Sin    4 0 r

This equation can be solved by separation of variable technique

ψ(r,,) = R(r) ()() Radial part

ψ(r,,) = R(r)() () Angular part

ψ(r,,) = R(r) ()() Angular part

Solution may be a product of three 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.
Electron described by a particular wavefunction is
said to occupy that orbital.
Atomic orbitals specified by three quantum numbers
n, l, and ml.
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Orbital angular momentum = [l(l+1)]ħ
Principal quantum numbers, n: Energy Levels

The energy levels are

En = e4Z2/32ħn2
= hcRZ2/n2 where
Where R = (e4/32ħ)/hc

Energy is –ve  stabilization effect

Higher the value of Z  more
stabilization
When n increases energy
increases
Solution : Some example
For l=0, ml =0
For n=1, l =0
3 1
1 2
  1  2
R(n,l) = 2  e 2 Y l, ml (,)=  
 a0   4 

 Y is a constant and does not depend on  and 

 For a given radial distance, same value of probability is
observed at all directions from nucleus
 S-orbitals are spherically symmetrical
Solution :
For n=2, l =1 For l=1, ml =0 , +1, -1
1
3  3  2
R(n,l) = 1 1 
   e 4
2
Y1,0 ( ,  )    cos 
4 6  a0   4 
1
 3  2
   sin  e i
 8 

 The angular variation of wavefunction 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)
 Atomic Orbitals
• Principal Quantum Number (n) = the
energy level of the electron.
• Within each energy level the complex math
of Schrödinger's equation describes several
shapes.
• These are called atomic orbitals
• Regions where there is a high probability of
finding an electron.
 S orbitals
• 1 s orbital for every energy level
• Spherical
shaped

• Each s orbital can hold 2 electrons

• Called the 1s, 2s, 3s, etc.. orbitals.
 P orbitals
• Start at the second energy level
• 3 different directions
• 3 different shapes (dumbell)
• Each can hold 2 electrons
 D orbitals
• Start at the third energy level
• 5 different shapes
• Each can hold 2 electrons
 F orbitals
• Start at the fourth energy level
• Have seven different shapes; 2 electrons per shape