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2.57 Nano-to-Macro Transport Processes

Quick review of Lecture 3

Photon: E = hν , p = h / λ .

Fall 2004

Lecture 4

Assuming Ψ t (r,t)=Ψ(r)Y(t), we use separation of variables to solve the Schrödinger

equation

2

Ψ

t

2

m

t

∇ Ψ + U Ψ = i

t

t

2

.

The solutions are

Y C

=

1

exp

E

−=

i

t

C

1

exp

[

it ω

]

,

and

2

2 m

∇ Ψ+ − Ψ= 0 ,

U E

2

(

)

where the eigen value E represents the total energy of the system.

Heisenberg uncertainty principle states

< ∆px >< ∆ >≥ < ∆tE >< ∆ >≥ .

;

2

2

2.3 Example solutions:

Here we determine u ( r )

(,)

by the boundary conditions and will not consider the urt

case.

2.3.1

Free particles in 1D

In this case, there are no constraints for the particles. The potential energy u=0 so that

d Ψ

2

2

2 m dx

2

− Ψ= 0 .

E

This gives

ψ Ae

=

ikx

+

Be

ikx

,

2.57 Nano-to-Macro Transport Processes Quick review of Lecture 3 Photon: E = h ν , p

where k = 2/ mE = p / (note

(,)

Ψ=

t

x t

Ae

()

t kx

i

−+ ω

+

Be

()

−− ω

i

t kx

,

Ep

=

  • 2 / 2 m ). The final solution is

in which the first term corresponds to negative-direction propagation, the second term is

positive-direction wave. Please also recall problem 2.5 in assignment 2.

2.3.2

Quantum well

Consider the general case of a particle in a one-dimensional potential well, which can be,

for example, an electron subject to an electric potential field as shown in the figure. This

is actually the model for thin films. The steady-state Schrödinger equation for the particle

in such a potential profile is

d Ψ

2

2

2 m dx

2

E

Ψ= 0 (0<x<D); Ψ = 0 (x<0 or x>D).

Note: for u → ∞ (x<0 or x>D), only Ψ = 0 can satisfy the Schrödinger equation.

U = ∞

= ∞ Potential

Potential

 

Particle

   
= ∞ Potential Particle U=0 D x
= ∞ Potential Particle U=0 D x
 

U=0

D

x

Same as the free particles, the solution for first equation is still

− ikx ikx Ψ= Ae + Be , 2 mE 2 mE p where k ===
− ikx
ikx
Ψ=
Ae
+
Be
,
2 mE
2 mE
p
where
k ===
.
2

The general boundary conditions are the continuity of the wave functions and their first

derivatives at the boundaries. The latter derives from the continuity of particle flux at the

boundary. For the current problem, the continuity of the first derivatives is not required

because the wavefunction at the boundaries are already known to be zero. With the

continuity of the wave function at x=0 and x=D, we have

Note: for u → ∞ (x<0 or x>D), only Ψ = 0 can satisfy the Schrödinger

x=0

A+B=0

x=D

A exp [+

ikD B exp [ikD ] = 0

]

Above equations yield

(

Ae

ikD

ikD

e

)0

=

.

Noticing A 0 , we obtain sin(kD)=0 . Thus

k D=nπ (n=0, ± 1, ± 2 ) n or 2 mE 1 ⎛ π n
k
D=nπ (n=0, ± 1, ± 2 )
n
or
2
mE
1
π n
n
D
= nπ
, energy eigen value
E
=
2
n
2m
D

2

.

The material wave function inside the potential well is

Ψ

n

n π x

D

= − 2iA sin

,

which is identical with the previous results of standing wave.

Note: for n, obviously it is not zero. Since solutions of negative n values are equivalent to

those of positive values, here we can just let n=1, 2

Normalization is still used to calculate A, i.e.

D

0

*

ΨΨ x x dx =

t

()

t

()

1 .

Finally we get

A = i

1 2 D
1
2 D

.

2.3.2 Particle in a 2D box

y

U=
U=

U = ∞

x
x
 

0

O

2

∂ Ψ ∂ Ψ

2

2

+

D

E Ψ = 0

 

1

2

m

x

2

y

2

2

d X

+

1

2

d Y

+

2 mE

= 0 .

 

.

X

dx

2

Y

dy

2

2

 

2

1dX

X

dx

2

2

= − k ,

x

2

1dY

Y dx

2

2

= − k .

y

The solution for X is

X ()

x

= sk +

A in

x

x

(

)

Bcos

(

k

x

x

)

.

k

=

π

n

D

(

n

=

1,2,3

 

)

 

x

.

Similarly,

k

y

=

l

π

D

(

l

 

1,2,3

 

)

=

 

Thus

.

We establish a coordinate system as shown in the schematic above. Clearly, outside the

potential well, we have Ψ = 0 because U = ∞ . We thus focus on the solution inside the

potential well. The Schrödinger equation inside the well (U=0) is

We still use the separation-of-variables technique. Assuming Ψ (x , y ) = X ( x )Y ( y ) and

substituting into the above equation leads to

In the above equation, the first term depends on x and the second term on y. The third

term is a constant. This leads to the requirement that both the first and the second term

must each be a constant. Since E is positive, we can prove neither of the first two terms

can be positive. Errors will occur if we let one of them be positive. Thus, we write

To satisfy the boundary condition that Ψ =0 at x=0 and x=D, we must have X=0 at x=0

and x=D. Applying these boundary conditions, we see that

E

 

=

(

2

+

n

2

) π

2

2

( ,n=1,2,…)

 

n

2

mD

2

 

and

 

Ψ

=

C

nπx ⎞ ⎛ πy

sin

sin

n

n

D

D

.

We can further determine the constant C n =2/D.

 

For quantum numbers: n, l, …

 
 

(1)

n=1, l=2, E 12 ,

Ψ

12

(2)

n=2, l=1, E 21 ,

Ψ

21

Note:

E 12 =

E 21, but

Ψ

12

and

Ψ

21

are

flipped

in

the

x

and

y

directions from

Ψ

 

=

C

 

nπx ⎞ ⎛ πy

sin

sin

. These states that have different wavefunctions but the

n

n

D

D

same energy are said to be degenerate. The degeneracy of an energy state is the number

of wavefunctions having the same energy.

  • 2.3.3 Electron spin & Pauli exclusion principle

Each wavefunction obtained in the previous sections represents a possible quantum

mechanical state at which a particle can exist under the given potential. The solution of

the Schrödinger equation, however, does not tell the whole story on the quantum state of

a particle. For example it cannot distinguish the spin of particles. For electrons,

corresponding to each wavefunction obtained from the Schördinger equation, there are

two quantum states (or two relativistic wavefunctions), which are usually denoted by an

additional quantum number s that can have the following values:

 

1

1

s =

2

or

2

,

where s=1/2 is called spin up and s=-1/2 is called spin down.

The Pauli exclusion principle says that each quantum state can be occupied by at most

one electron.

2.3.4

Other potentials

(1) Harmonic oscillator

From

F

Kx

=− =−

du

dx

,

we

equation becomes

22

d

Ψ

+

Kx

2

− Ψ=

E

2

m dx

2

which gives

(

E

n

2

)0 ,

hn

=+

ν

(

1/ 2);

have

1

u = Kx

  • 2 (shown in the figure). The Schrödinger
    2

1 K ν = . 2 π m
1
K
ν
=
.
2
π
m

Note: the zero point (intrinsic) energy

hν

is required by the Heisenberg uncertainty
2

principle ( < ∆t >< ∆E >≥ ). It shows that the oscillator has some energy even at the rest.

2

Note: the zero point (intrinsic) energy is required by the Heisenberg uncertainty 2 principle ( <
u
u

x

Note: to calculate the intrinsic frequency for diatomic molecules with two atoms of mass

m 1 and m 2 , the reduced mass should be used,

m =

m m

1

2

.

m +

1

m 2 -e e
m
2
-e
e
u r
u
r

Now consider the case that an electron moves around the nucleus, which is assumed to be

stationary. The interaction between the nucleus and the orbiting electron is governed by

the Coulomb force

F =−

1

2

e

du

=−

4

πε

o

r

2

dr

,

where ε o =1.124x10 -10 /4π [C 2 /(m 2 N)] is the electrical permittivity of the vacuum. It yields

u ( r ) = −

2

e

4

πε

0

r

.

Using separation of variables, we assume

Ψ

n m

= R r Y

n

(

)

m

(θ , ϕ )

.

energy levels of the electron-nucleus system are

el

E =−

n

Mc

  • 2 13.6 eV

  • 1 =−

  • 2

22

n

2

n

(,

n 1

n + 1 and

m
m

, =0, 1, 2, …)

The allowable

in which M is the electron mass. For quantum number n=1, we have

n=1, l=0, m=0,

Ψ

  • 100 , s (two quantum states determined by spin), 1s orbital.

  • l m

=

0

=

0

  • l m

=

1

= −

1,0,1

n=2--->

2 s orbital

2 p orbital

Basically there are four wave functions for n=2 and totally eight quantum states. The

energy levels of different orbitals are drawn in the following figure. The spherical s

orbital and dumb-bell p orbitals are also presented here. The degeneracy is determined by

 

g=2n

2

.

E

g=2n 2 . E 3s 3p 3d n=3 2s 1s 2p n=2 (-1.5 eV) (-3.4 eV)
 

3s

3p

3d

n=3

2s 1s
2s
1s
 
2p
2p

n=2

(-1.5 eV)

(-3.4 eV)

n=1

 

(- 13.6 eV)

 
s orbitals
s orbitals
p orbitals
p orbitals

Note: the energy gap between different n values is much larger than the thermal energy

(k B T~26 meV) and it is almost impossible to thermally excite electrons to a higher n level.

A stable element is obtained only if all the orbitals for the highest n are completely filled,

such as He.

Now one may wonder why the energy eigenvalue E has different relationships with n.

Here we will give a simple argument, without solving the Schrodinger equation, to show

that this is indeed the case. My argument is based on the requirement of forming

standing waves in given potential. For harmonic oscillators, as shown in the following

figure, the standing waves inside the potential, assuming at the boundaries, wavefunction

is zero, give

λ n x = . n 4 1 h 1 hn 2 22 Kinetic energy is
λ
n
x =
.
n
4
1
h
1
hn
2
22
Kinetic energy is
KE p
==
/2
m
(
)
=
(
)
.
2
m
λ
24
mx
n
u
u
r
n=2
n=1
x
x 1
x 2

Equating the kinetic and potential energies (sort of equipartition of energy, but only a

hand waving argument), we obtain

K

 

2

1

hn

)

2

 

=

 

x

(

2

n

24

m

x

n

or

 

2

1

1/2

nh

 

x

n

= (

Km

)

Thus

4

.

E Kx

2

n

=

nh K 4 m
nh K
4
m

,

which is a linear functions of n, similar to what we obtain from solving Schrodinger

equation. Similarly, we can deal with electrons moving around the nucleus but changing

the potential energy to

u

2

e

=

4

πε x

0

n

. Finally we get

E

1

2

n

.

Rigid rotation

In classic mechanics, the angular momentum is expressed as r × p . However, because of

the uncertainty principle, it is difficult to give such an expression in quantum mechanics.

In classical mechanics, a quantity often used to describe the rotation is the moment of

inertia. For a two-mass system rotating relative to its mass center, the moment of inertia

is

I

=

m

1

m

2

2

r

o

m

1

+

m

2

where r o is the effective separation between the two atoms.

ω m 1 m 2
ω
m 1
m 2

The energy eigenvalues are

E l =

2

  • 2 I

(

+

1)

=

hB

(

+

1)

(for |m| , =0,1,2, …).

Note: the discussion on harmonic oscillators

and

rigid rotors gives other useful

information. For example, we can calculate the spring constant of an oscillator by

measured vibrational frequency, from

1 K ν = . 2 π m
1
K
ν
=
.
2
π
m