From Bohr to Schrödinger

† Confinement or Boundary
† Energy
† Energy Staircase
† Probability

† Quantum Well, Quantum Wire, Quantum Dot

† Semiconductor, Doping, Band Gap, Fermi Energy
† Metals, Organic Metals, Nevil Mott

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Wave equation [Schrödinger Equation]

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An Electron Wave is similar to Waves of Light, Sound & String

Wave motion of a String: Amplitude vs. Position


1.0

0.5
t=0
t =1/8T
0.0
t =1/4T
y

-0.5 A t = 1/2T
-1.0

0 2 4 6 8 10
x 3
 Derivation of wave equation
y = A sin (wt – f)
w = angular vel.; f =phase;  = wave length

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w= angular vel.
f = phase
 = wave length
Derivation of wave equation

y = A sin (wt – f)
w = 2p/T = 2pn = 2pv/ [n = v/]
phase diff/path diff = f/x = 2p/; f = 2px/
y = A sin [(2pv/)t – (2px/)] = A sin (2p/) [vt – x]
by differentiating w.r.t. x at constant t, we get
d2y/dx2 + (4p2/2) y = 0 a wave eqn.

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 d2y/dx2 + (4p2/ 2) y = 0
Look at y in another way
d2y/dx2 + (k2) y = 0
y = B’ expikx+B’’exp-ikx {expim = cos(m) + i sin(m)}
y = C’Cos(kx) + C’’Sin(kx)

• In three dimension the wave equation becomes:

d2y/dx2 + d2y/dy2 + d2y/dz2 + (4p2/2)y = 0
• It can be written as 2y + (4p2/2)y = 0
• We have  = h/mv
• 2y + (4p2m2v2/h2) y = 0

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Energy of a matter wave is present in its wave equation

· 2y + (4p2m2v2/h2) y = 0
· E = T + V or T = (E-V) (E = total energy)
· V = Potential energy, T = Kinetic energy
· T = 1/2 mv2 = m2v2/2m
· m2v2 = 2m(E-V)
· 2y + (8p2m/ h2)(E - V) y = 0

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 2y + (8p2m/ h2)(E - V) y = 0

• This can be rearranged as

• (- h2/8p2m) 2 + V}y = Ey
• Hy = E y
 H = [(- h2/8p2m)2 + V) Hamiltonian operator

{(-h2/8p2m)(2/x2 + 2/y2 + 2/z2) + V}  = E 

d2y/dx2 + (4p2/ 2) y = 0

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{(-h2/8p2m)(2/x2 + 2/y2 + 2/z2) + V}  = E 

the operator for total energy = Hamiltonian operator H

H = E

Microscopic World: “Wave Mechanics is the God”

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Q. How to find energy of H-like atom?

Ans. Simple. From Wave Equation but be careful

about Hamiltonian.

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 How to write Hamiltonian for different systems?
{(-h2/8p2m)2 + V}  = E 

Hydrogen atom
• V = -e2/r, (r = distance between the elec & nucl)
• H = {(-h2/8p2m) 2 –e2/r}
• 2  + (8p2 m/h2)(E+e2/r)  = 0
• If the effective nuclear charge is Ze
• H = {(-h2/8p2m )2 – Ze2/r}

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 +
e (x,y,z)
H2
{(-h2/8p2m)2 + V}  = E  ra rb

A(+e) Rab B(+e)

• PE = V = -e2/ra – e2/rb + e2/Rab
• H = (-h2/8p2m)2 + ( – e2/ra - e2/rb + e2/Rab)
• The Wave equation is
• 2  + (8p2 m/h2) (E+ e2/ra + e2/rb – e2/Rab)  = 0

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 e1 (x1, y1, z1)
He Atom
r12
r1

e2 (x2, y2, z2) r2 Nucleus (+2e)

{(-h2/8p2m)2 + V}  = E 

• V = -2e2/r1 – 2e2/r2 + e2/r12

• H = (-h2/8p2m) (12 + 22) + V
• The Wave equation is
• (12 + 22 ) + (8p2 m/h2)(E-V)  = 0
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 e1 (x1, y1, z1) r12 e2 (x2, y2, z2)
ra2
H2 r
a1 rb2
rb1
A(+e) Rab B(+e)

• PE = V = ?
• H = (-h2/8p2m)(12 + 22) + V
• The Wave equation is
• (12 + 22 ) + (8p2 m/h2)(E-V)  = 0
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An Electron in One Dimensional Box

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A matter particle-wave in a One Dimensional Box
Wave eqn
Length =a
d2  /dx2 + (8p2 m/h2)(E-V)  = 0
V=0
Boundary Conditions:
x x 1. V=0 &  = 0 between x=0 & x=a
=0 =a
2. V= at x=0 & x=a & outside 1DB
d2/dx2 + [8p2mE/h2]  = 0
in Hcap = E form:
[(-h2/8p2m)(2/x2)]  = E
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A matter particle-wave in a One Dimensional Box

Length =a • d2/dx2 + [8p2mE/h2]  = 0

• Put k2 = 8p2mE/h2
V=0
• d2/dx2 + k2 = 0
x x
=0 =a • Solution:  = C cos kx + D sin kx

• Apply Boundary conditions:

•  = 0 at x = 0  C = 0
  = D sin kx

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A matter particle-wave in a One Dimensional Box

Length =a
•  = D sin kx
• Apply Boundary Condition:
V=0 •  = 0 at x = a,  D sin ka = 0
x x • sin ka = 0 or ka = np,
=0 =a
• n = 0, 1, 2, 3, 4 . . .
n = D sin (np/a)x
k2 = 8p2m/h2[E] E = k2h2/ 8p2m = n2 h2/ 8ma2
n = 0 not acceptable: n = 0 at all x
Lowest kinetic Energy = E1 = h2/8ma2
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A matter particle-wave in a One Dimensional Box
a
V= V =  • n = D sin (np/a)x
• En = n2 h2/ 8ma2
• n = 1, 2, 3, . . .
• E1 = h2/8ma2 , n=1
• E2 = 4h2/8ma2 , n=2
• E3 = 9h2/8ma2 , n=3

x=0 x=a Energy is quantized

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A matter particle-wave in a One Dimensional Box

What about ?
n = D sin kx

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 How about ? n = D sin kx

• Normalize n = D sin (np/a)x

• Ans: (2/a)½ sin (np/a)x

x=0 x=a

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 How about ?

• In Newtonian Mechanics, square of

amplitude is intensity
• By analogy y2  density/probability of
finding the matter-wave in the space.
• If (x, y, z) is the probability function,
•  (x, y, z)  2 (x, y, z)
 d = 1  2 d = 1

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An Electron in One Dimensional Box : Example

H2C6=C5H—C4H=C3H—C2H=C1H2

H2C6=C5H—C4H=C3H—C2H=C1H2

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Estimating pigment length

L = 7 x 1.2 = 8.4 A

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Wavelength of transition for Anthracene
Particle in a Box
Simple model of molecular energy levels.

p electrons – consider “free”

in box of length L.
Ignore all coulomb interactions.

Anthracene
L 
L6 A

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 An Electron in an Atom

Similar treatment as particle in a box:

End result is quantization of energy

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 QM to Atom
From H  = E  to Quantized Energy

Eatom= -(hcZ2)/n2 in Rydberg unit

Birth of Quantum No.

 =  radial x  angular

H He+ 27
 y : From Mathematics to Real Life
Heisenberg’s Uncertainty principle:
http://www.aip.org/history/heisenberg/p08.htm

Our knowledge of the

position of a particle

can never be absolute
h/
Born: “Can we interpret y in terms of probability?
Yes, we can.”

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 y : From Mathematics to Real Life

MAX BORN Characteristics

of
Wave Function

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 Characteristics of Wave Function:
What Prof. Born Said
• In Classical mechanics, square of wave
amplitude is a measure of radiation intensity
• In a similar way, y2 or y y* may be related
to density or appropriately the probability of
finding the electron in the space.
• Let  (x, y, z) be the probability function,
• ƒ d = 1

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 Characteristics of Wave Function:
What Prof. Born Said
• Let  (x, y, z) be the solution of the wave
equation for the wave function of an electron.
Then we may anticipate that
•  (x, y, z)  2 (x, y, z)
•  (x, y, z) = 2 (x, y, z)
 2 d = 1

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 Characteristics of Wave Function:
What Prof. Born Said
•2 d = 1
•If  is complex then replace 2 by *
Normalizing a wave function
•If we find that
•2 d = 1/N2
•then N2 2 d = 1
•N is termed as Normalization Constant
Normalize n = D sin (np/a)x

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 From Cartesian to Polar

wave function ψ(x,y,z)

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The wave equation in Polar Coordinate

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Energy of Hydrogen like atom

-2Z2e4μ = -Z2e2 ao = h 2
n2h2 2aon2 4 μ e2
μH = 0.9994557me
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Check out Atkins, or
any QM Book, or
Wiki, or Google

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Radial distribution function: 4pr22

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Angular distribution functions

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 Atomic Orbital: Two faces of 
 radial  angular

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