BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 3

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 Summary (Lecture 2)
1  1 1 
Line Spectra of hydrogen atom:    RH  2  2 
~
-1   n1 n2 
Expt. n > n ; R = 109737.315 cm
2 1 H

Bohr’s model of H atom:

L = mevr = nh/2π =nħ, n=1,2,3,…
(quantization of angular momentum)
Only those orbits which obey the above condition
are stable and do not radiate energy.
Transition between orbits give rise to absorption/
emission of light. E  h me e 4
~ 
1

E2  E1  RH 
 hc 8 02 h3c
2
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 Summary (Lecture 2)

de Broglie Relation: p = h/

Matter wave- linear momentum is inversely related
to wavelength.
Heisenberg’s uncertainty principle:
px x  ħ/2
Time-dependent wave function.
 (x,y,z,t) = ψ(x,y,z) f(t)

P= * dV = 2 dV Total Probability between a & b

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 Summary (Lecture 2)

 all space 2 dτ = 1 - Born Interpretation

Requirements of : Square integrable-

Normalizable;  must be single valued & Bounded;
 and d/dx must be continuous
Schrodinger Equation:

For a single particle of mass “m” moving with

energy “E” in one dimension (x).
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 Summary (Lecture 2)

 2   2 2 2  
  2  2  2   V ( x, y, z ) ( x, y, z )  E ( x, y, z )
 2m  x y z  

Ĥ = E
Ĥ is the Hamiltonian operator or total energy
operator.

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 Summary (Lecture 2)

For every physically observable property, we will have

anobservable
Every operator whichmechanics
in quantum operates on the wavefunction
is represented by an operator which and
is used to
gives
obtain as ainformation
physical result the property’s
about the observablevalue. Examples
from the are For an
state function.
observable
giventhat is represented in classical physics by a function Q(x,p), the corresponding
below.
 
operator is Q( x , p ) .
Observable Operator

Position x
Momentum   
p
i x
Energy 
p2  2  2
E  V ( x)    V ( x)
2m 2m x 2

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Postulates of Quantum Mechanics

• Postulate 1: The state of a system is described completely

in terms of a state vector (r, t), which is quadratically
integrable. , first derivative of  , and second derivative of
 are continuous, single valued, finite.

• Postulate 2: To every physically observable property there

exist a linear Hermitian operator. (Real values)

• Postulate 3: In any measurement of the observable

associated with operator Â, the only values that will ever be
observed are the eigenvalues ai, which satisfy the
eigenvalue equation  gi = aigi.
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Postulates of Quantum Mechanics

Postulate 4: The eigenfunctions of operators

corresponding to observable forms a complete set.

Postulate 5: If a system is in a state described by a

normalized wavefunction , then the average value of the
observable corresponding to  is given by

< A >=

 * Â d

• Postulate 6: The wavefunction or state function of a

system evolves in time according to the time-dependent
Schrodinger equation ˆ
H ( r , t )  i ( h / 2 )( / t )

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Next What ?

? How to extract information from the solutions

? How to solve schrödinger equation for the system
? How to define wavefunction of any system ?
 General form of Schrödinger Equation
 Observables & Operators
 Acceptable wavefunction
 Need for Quantum Mechanics

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Application to a Microscopic system
Translation Motion in 1-Dimension: Particle in a Box
Consider a particle of mass m travelling along x-axis,
confined to a length L by infinite potential barriers at x = 0
and x = L (infinitely deep potential well)

V=0 For x < 0 and x > L,

 = 0 since
probability of finding
the particle in these
V= V =  regions is zero.

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 Particle in one-dimension box
Bead free to slide
between two stops

QM: wave associated

with particle
 = sin kx or cos kx or
a combination of both

Boundary conditions must be

satisfied by the wavefunctions

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 Particle in 1-D box: Wavefunction

Let the trial wavefunction be  ( x)  A sin kx  B cos kx

Applying the boundary condition at x = 0 and L gives
 (0)  0  B cos k 0  0  B  0

 ( L)  0  A sin kL  B cos kL  0
So, we obtain: A sin kL  0
Now A  0; otherwise  will be 0 everywhere.
Hence,
sin kL  0,  kL  n n  1,2,3,
n cannot be 0
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Particle in 1-D box: Normalized wavefunction

The wave function for the system will be

n
 ( x)  A sin x n  1,2,3, 
L
Now, if (x) is normalized wave function then
nx nx
L L

0  * ( x) ( x)dx   ( A sin L ) * ( A sin L )dx  1

0

nx
L
A  sin
2 2
dx  1 Solution gives A2L/2 =1
0
L or A = (2/L)1/2

2  n 
Normalized wave function for particle  ( x)  sin  x
in a 1-D Box L  L 
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Particle in 1-D box: Normalized wavefunction

Normalized wave function for particle

in a 1-D Box

2  n 
 ( x)  sin  x
L  L 
n = 1, 2, 3….

The boundary conditions bring

in quantization.

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 Particle in 1-D box: Calculating Energy
2  n  Ĥ=E
 ( x)  sin  x
L  L 

2 d 2 2 d 2  2  n 
 2
 ( x )  2 
sin  x 
2m dx 2m dx  L  L 
2 n 2 d   n 
  cos x 
2mL L dx   L 
h2n2  2  n  h2n2
 2 
sin  x   [ ( x)]
8mL  L  L  8mL 2

n2h2
En  n = 1, 2, …
8mL2
Quantized energies of the paricle in a 1-D box; n: quantum number
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Ground State Wavefunction and Energy

2  1 
1  sin  x
L  L 
12 h 2
En 1  2
8mL
n2h2 p2 If ‘n’ = 0; then  = 0 everywhere and particle
En  2
 vanishes (Not possible).
8mL 2m
h nh The energy at lowest cannot be zero;
p 
 2L consequence of uncertainty principle: particle
is within the box, so uncertainty in position,
2L x cannot be infinite; px (or energy) cannot

n be zero.
Ground state energy: h2/8mL2 :Zero point energy
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Plot of wavefunctions vs position
 = 2L/n; where n = 1,2,3,4……

 = 2L/3  = L/2
2  3  2  4 
3  sin  x 4  sin  x
L  L  L  L 

 = 2L =L
2  1  2  2 
1  sin  x 2  sin  x
L  L  L  L 

• The wavefunctions are all symmetric or antisymmetric about the

midpoint of the box
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Probability Amplitude (b) & Density (c)

32 h 2
E3   9 E1
8mL 2 node

22 h 2
E2  2
 4 E1
8mL

12 h 2
E1 
8mL2

n – 1 nodes in n, energy increases with increasing

number of nodes, no nodes in ground state
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Classical Limit
n2h2 (i) E depend on ‘L’, the size of the system and ‘m’,
En  the mass of the particle.
8mL2
(ii) Greater the value of L or m, the less important
are the effects of quantization on translational
motion: classical limit
(iii) As n becomes very large, the probability
distribution becomes uniform (continuous)
over the entire length of the box.

At sufficiently high energies, the quantum

mechanics agrees with classical mechanics.
Correspondence principle

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Particle in two dimensional (2-D) box

A two-dimensional square
well.
Potential energy is zero
between x = 0 and x = L1 and
y= 0 and y = L2,
Rises sharply to infinity at the
walls.
 ( x, y )  X ( x).Y ( y )

Ĥx X(x) = Ex X(x)
Ĥy Y(y) = Ey Y(y) E= Ex + Ey
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 Particle in 2-D box: Schrödinger Equation
2  d 2 d2 
  2  2  ( x, y )  ( E x  E y ) ( x, y )
2m  dx dy 

On Solving
2 2  nxx   n yy 
 ( x, y )  sin   sin  
L1 L2  L1   L2 
2 2 2 2
nx h n h Where nx= 1,2,3….;
E  
y
2 2
8mL1 8mL2
ny=1,2,3…
nx= 1 & ny=1 : Ground state energy of particle in 2-D box (square)
(nx  n y )h 2 Discussion & Interpretation
2 2
Now, when L1 = L2
E  in Tut. Sections
8mL2
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 Particle in 2-D box (square): Wavefunctions
2  2x   2y 
 2 , 2 ( x, y )  sin   sin  
L  L   L 
E2, 2 8h 2
E2 , 2 
Non Degenerate state 8mL2

2  x   2y 
 1, 2 ( x, y )  sin   sin  
L L  L 
2  2x   y 
 2,1 ( x, y )  sin   sin  
L  L  L
E2, 1 E1, 2 5h 2
E1, 2  E2,1 
Doubly Degenerate states 8mL2
2-fold degenerate
Discussion & Interpretation
in Tut. Sections
2  x   y 
 1,1 ( x, y )  sin   sin   E1, 1 2h 2
L L L E1,1  2
Non Degenerate state 8mL

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