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3.012 Fund of Mat Sci: Bonding – Lecture 2

THINK OUT OF THE BOX

@Bobby Douglas, from photo.net

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

Last time: Wave mechanics

1. Classical harmonic oscillator

2. Kinetic and potential energy

3. De Broglie relation λ • p = h

4. “Plane wave”

5. Time-dependent Schrödinger’s equation

6. A free electron satisfies it

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

Homework for Wed 14

• Study: 15.1, 15.2

• Read: 14.1-14.4

• Office Hours – Monday 4-5 pm

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

Time-dependent Schrödinger’s equation

(Newton’s 2 nd law for quantum objects)

• An electron is fully described by a wavefunction – all the properties of the electron can be extracted from it

• The wavefunction is determined by the differential equation

r 2 h ∂Ψ r , t ( ) 2 − ∇Ψ ( r r
r
2
h
∂Ψ r , t
(
)
2
− ∇Ψ
(
r r , t
)
+
V ( r r , t
)
Ψ
(
r r , t
)
=
i h
2 m
∂ t
) + V ( r r , t ) Ψ ( r r , t )

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

Stationary Schrödinger’s Equation (I)

r 2 h r ∂Ψ r , t ( ) 2 − ∇Ψ ( r
r
2
h
r
∂Ψ r , t
(
)
2
− ∇Ψ
(
r r , t
)
+
V r t
(
,
*
)
Ψ
(
r r , t
)
=
i h
2 m
∂ t
+ V r t ( , * ) Ψ ( r r , t ) =

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

Stationary Schrödinger’s Equation (II)

Stationary Schrödinger’s Equation (II) ∇ + V ( r r ⎤ ) ( ) = ϕ
Stationary Schrödinger’s Equation (II) ∇ + V ( r r ⎤ ) ( ) = ϕ
Stationary Schrödinger’s Equation (II) ∇ + V ( r r ⎤ ) ( ) = ϕ
Stationary Schrödinger’s Equation (II) ∇ + V ( r r ⎤ ) ( ) = ϕ
∇ + V ( r r ⎤ ) ( ) = ϕ ( ) ⎢
∇ + V ( r r ⎤
)
(
)
= ϕ
(
)
⎥ ϕ
2 m

h

2

2

r r

E

r r

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

Stationary Schrödinger’s Equation (III)

h

2

2 m

2

∇ +

V r r ⎤ ⎥ ⎦

(

)

(

ϕ

r r

)

=

E r r

(

ϕ

)

1. It’s not proven – it’s postulated, and it is confirmed experimentally

2. It’s an “eigenvalue” equation: it has a solution only for certain values (discrete, or continuum intervals) of E

3. For those eigenvalues, the solution (“eigenstate”, or “eigenfunction”) is the complete descriptor of the electron in its equilibrium ground state, in a potenitial V(r).

4. As with all differential equations, boundary conditions must be specified

5. Square modulus of the wavefunction = probability of finding an electron

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

From classical mechanics to operators

• Total energy is T+V (Hamiltonian is kinetic + potential)

r p → r gradient operator − i h ∇ r r →
r
p
r
gradient operator
− i h ∇
r
r

rˆ

• classical momentum

• classical position

multiplicative operator

→ • classical position → multiplicative operator 3.012 Fundamentals of Materials Science: Bonding - Nicola

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

Operators, eigenvalues, eigenfunctions

Operators, eigenvalues, eigenfunctions 3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

Free particle: Ψ(x,t)=φ(x)f(t)

2

 

h

2

m

2

ϕ = ϕ

x

E

(

)

(

x

)

i h

d

f

(t )

=

E f (t )

     

dt

f ( t ) = E f ( t )       dt 3.012 Fundamentals
f ( t ) = E f ( t )       dt 3.012 Fundamentals

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

Infinite Square Well (I) (particle in a 1-dim box)

2

h d

2

ϕ

(

x

)

2 m d x

2

= E

ϕ

(

)

x

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

Infinite Square Well (II)

Infinite Square Well (II) 3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)

Infinite Square Well (III)

Energy 20 18 16 14 12 10 8 6 4 2 0
Energy 20 18 16 14 12 10 8 6 4 2 0
Energy 20 18 16 14 12 10 8 6 4 2 0
Energy 20 18 16 14 12 10 8 6 4 2 0
Energy 20 18 16 14 12 10 8 6 4 2 0

Energy

20

18

16

14

12

10

8

6

4

2

0

Energy 20 18 16 14 12 10 8 6 4 2 0
Energy 20 18 16 14 12 10 8 6 4 2 0
Energy 20 18 16 14 12 10 8 6 4 2 0

Figure by MIT OCW.

Energy or wave function value 20 18 16 14 12 10 8 6 4 2
Energy or wave function value 20 18 16 14 12 10 8 6 4 2
Energy or wave function value 20 18 16 14 12 10 8 6 4 2
Energy or wave function value 20 18 16 14 12 10 8 6 4 2
Energy or wave function value 20 18 16 14 12 10 8 6 4 2

Energy or wave function value

20 18 16 14 12 10 8 6 4 2 0 0.0 0.2 0.4 0.6
20
18
16
14
12
10
8
6
4
2
0
0.0
0.2
0.4
0.6
0.8
1.0

x/a

Energy or wave function value 20 18 16 14 12 10 8 6 4 2 0
Energy or wave function value 20 18 16 14 12 10 8 6 4 2 0
Energy or wave function value 20 18 16 14 12 10 8 6 4 2 0

Figure by MIT OCW.

3.012 Fundamentals of Materials Science: Bonding - Nicola Marzari (MIT, Fall 2005)