Lecture 5: Expectation

values and the particle in

a box v

Friday, January 19, 2024

 The importance of operators and eigenvalues
• Each classical observable (position, momentum, Energy etc.) of a system has a quantum mechanical operator
associated with it.
• The eigenvalues of those operators are all that can be measured!
 Some properties of quantum-mechanical operators

1. Eigenvalues of Hermitian operators are real

2. Eigenfunctions of Hermitian operators are orthonormal

3. Operators are associative but they generally are not commutative (like matrices!)

Operators that do commute with each other are special. We will see this relates to the precision at which two observables
can be measured simultaneously (Heisenberg Uncertainty principle)
 Summary from lecture 4:
The Time-dependent Schrödinger Equation
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iEt/~
Ĥ (x, t) = i~ (x, t) = (x)e
@t
Operators
 Summary from lecture 4:
The Time-dependent Schrödinger Equation
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iEt/~
Ĥ (x, t) = i~ (x, t) = (x)e
@t
Operators
• Each classical observable has a Hermitian operator associated with it
∗
# 𝑑𝜏
! 𝜓 ∗𝐴∅ #
= ! ∅ 𝐴𝜓 𝑑𝜏

• Each operator has a set of eigenfunctions and eigenvalues (all that can be measured!)
# " = 𝑎" ∅"
𝐴∅
• Eigenvalues of Hermitian operators are real
• Eigenfunctions of Hermitian operators are orthonormal ! 𝜙!∗ 𝜙# 𝑑𝜏 = 𝛿!# - 𝐵0 = 𝐴- 𝐵-
𝐴, 0 𝐵0 𝐴- ≠ 0
• Operators generally do not commute (only in special cases!)

• Wavefunctions can be written in terms of superpositions of eigenfunctions of an operator

𝜓 = + 𝑐" ∅" ( |𝑐$ |% = 1 Probability of measuring a specific 𝑎$ ? |𝑐$ |% !

" $
Some examples
In-class Quiz
 Probability of measurement and expectation value
• Probability of a measurement outcome for some operator given the system has a wavefunction 𝜓?

𝜓 = + 𝑐" ∅" Calculate |𝑐$ |% !

"
 Probability of measurement and expectation value
• Probability of a measurement outcome for some operator given the system has a wavefunction 𝜓?

𝜓 = + 𝑐" ∅" Calculate |𝑐$ |% !

"
• How? Need to compute the overlap between wavefunction and eigenfunction of the operator!

𝑐$ = ! ∅∗$ 𝜓 𝑑𝜏
 Probability of measurement and expectation value
• Probability of a measurement outcome for some operator given the system has a wavefunction 𝜓?

𝜓 = + 𝑐" ∅" Calculate |𝑐$ |% !

"
• How? Need to compute the overlap between wavefunction and eigenfunction of the operator!

𝑐$ = ! ∅∗$ 𝜓 𝑑𝜏

• Outcome of individual experiment is still fundamentally random! What can we expect to measure on average
(repeating experiment many times)?

𝐴# = + 𝑎" |𝑐" |# Mean value or expectation value

"
 Probability of measurement and expectation value
• Probability of a measurement outcome for some operator given the system has a wavefunction 𝜓?

𝜓 = + 𝑐" ∅" Calculate |𝑐$ |% !

"
• How? Need to compute the overlap between wavefunction and eigenfunction of the operator!

𝑐$ = ! ∅∗$ 𝜓 𝑑𝜏

• Outcome of individual experiment is still fundamentally random! What can we expect to measure on average
(repeating experiment many times)?

𝐴# = + 𝑎" |𝑐" |# Mean value or expectation value

"

𝐴# = ! 𝜓 ∗ 𝐴𝜓
# 𝑑𝜏 For the position operator: 𝑥. = ! 𝜓 ∗ 𝑥𝜓
. 𝑑𝜏 = ! 𝑥𝜓 ∗ 𝜓 𝑑𝜏
 Standard deviation of an operator
• Sometimes we are interested not only in the mean measurement outcome but the spread of potential
measurement outcomes
• This can be achieved by computing the standard deviation of a measurement

% %
𝜎 % = 𝐴- % − 𝐴- =∫ 𝜓 ∗ 𝐴- % 𝜓 𝑑𝜏 − ∫ 𝜓 ∗ 𝐴- 𝜓 𝑑𝜏

𝜎 = standard deviation
𝜎 % = variance
Solving the Schrödinger equation: A particle in free
space (1D)
Solving the Schödinger equation: A particle in a 1D box

• Simple but powerful model system

• Explains optical excitation energies in polyaromatic
hydrocarbons and quantum dots

𝑉 𝑥 = 0 inside box
𝑉 𝑥 = ∞ outside box
 Solutions to the 1D particle in a box

ℎ% 𝑛%
𝐸$ =
8𝑚𝑎%

2 𝑛𝜋𝑥
𝜓$ 𝑥 = sin
𝑎 𝑎
Most likely vs average position of a particle in a box

What is the most likely position?

What is the average position?
THANK YOU v