Lecture 10 – Harmonic oscillator

Vibrational motion

Lecture 10:
Quantum-mechanical harmonic oscillator serves as the

basic model for molecular vibrations. Its solutions are
Harmonic Oscillator characterized by (a) uniform energy separation, (b)
zero-point energy, (c) larger probability at turning
points.

We introduce the concept of orthogonal polynomials.
Here, we encounter the first set: Hermite polynomials.

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Differential equations Vibrational motion

Quantum mechanical version of

a “spring and mass” problem.
Differential equations

The mass feels the force
proportional to the
displacement:
Custom-made solutions: F = – kx.
18th-19th
century Orthogonal polynomials
The potential energy is a
mathematical
geniuses harmonic potential:
Know, verify, and use V = ½kx2 (F = –∂V/∂x).
the solutions (thankfully) We

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Eigenvalues Comparison to
classical case

The Schrödinger equation is:
Quantum mechanical

 h2 d 2 1 2   1 k
 − 2m dx 2 + 2 kx̂  Ψ = EΨ Ev =  v +  hω , ω = , v = 0,1,2,
 2 m
Quantum number

If we solve this, we obtain the
Classical Same frequency
eigenvalues:
k
Amplitude x(t ) = A sin(ωt ), ω =
 1 k can take any m
Ev =  v +  hω , ω = , v = 0,1,2,
 2 m arbitrary
1 2 When the object stretches the spring
value, so
energy is not E= kA the most, the total energy is purely
quantized 2 potential energy

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Lecture 10 – Harmonic oscillator

Comparison to The energy levels

the particle in a box

The particle in a box Harmonic potential
Zero-point energy

Molecules never cease to
1 vibrate even at 0 K –
E0 = hω otherwise the uncertainty
2 principle would be
violated.

Energy separation

Ev+1 − Ev = hω
For molecular vibration, this amounts the energy of photon in
the infrared range. This is why many molecules absorb in the
infrared and get heated.

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Quantum in nature Quantum in nature

Vibrations of Vibrations of
CO2 Why is global H2O Why is water
warming? blue?

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Eigenfunctions Orthogonal polynomials

The Hermite polynomials are one

The eigenfunctions (wave functions) are example of orthogonal
1/4
polynomials.
Vibrational
2 x  h2 
They are discovered or invented Hermite wave function
Ψ v (x) = N v × H v ( y) × e − y /2 , y = , α =
α  mk  as the solutions of important
differential equations. They Radial part of
ensure orthogonality and Laguerre atomic wave
Normalization Gaussian function completeness of eigenfunctions. function
Hermite polynomial
Angular part

We do not have to memorize this precise form but we Legendre of atomic
wave function
must remember its overall structure: normalization
coefficient x Hermite polynomial x Gaussian function.

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Lecture 10 – Harmonic oscillator

The Hermite polynomials Ground-state

wave function

Since H0 = 1, the ground state

wave function is simply a
Gaussian function.

2 2
/ 2α 2
Ψ 0 ( x) = N 0e − y /2
= N 0e − x
1/4
x h2 
y= , α =
α  mk 

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The Hermite polynomials Verification

The Hermite polynomials have the following important
Second derivatives of a product of two functions
mathematical properties:

They are the solution of the differential equation:
d 2Hv dH v  h2 d 2 1 2  − y 2 /2
2
− 2y + 2vH v = 0  − 2m dx 2 + 2 kx  N v H v ( y)e
dy dy

They satisfy the recursion relation:
H v +1 − 2 yH v + 2vH v −1 = 0 d ( fg ) df dg

Orthogonality = g+ f
dx dx dx

( H e )( H e )dy = 0, v′ ≠ v
∞
d 2 ( fg ) d 2 f d 2g
∫
− y2 / 2 − y2 / 2 df dg
−∞
v′ v 2
= 2 g +2 +f
dx dx dx dx dx 2
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Verification Verification

Let us verify that this is indeed the eigenfunction.
Let us verify that this is indeed the eigenfunction.
Substituting Substituting

1/4 1/4
2 2
/ 2α 2  h2  2 2
/ 2α 2  h2 
Ψ 0 ( x) = N 0e − y /2
= N 0e − x y=
x
α
, α =
 mk 
Ψ 0 ( x) = N 0e − y /2
= N 0e − x y=
x
α
, α =
 mk 
into the Schrödinger equation, we find into the Schrödinger equation, we find
 h d 2 2
1 2 − x 2 /2 α 2
 h2 d 2 1 2  − x 2 /2 α 2
 h2 x 2 h2 1 1 2  2 2

 − 2m dx 2 + 2 kx  N 0 e =?  − 2m dx 2 + 2 kx  N 0e = − + + kx  N 0 e − x /2α
 2m α 
4
  2m α 2 2
 1 k 1 2
2 2 2 2
deax d (ax 2 ) de ax 2 deax d (ax 2 ) de ax 2
1
= = (2ax)e ax = = (2ax)e ax =  − kx 2 + h
2
+ kx  N 0e − x /2α
2

dx dx d (ax 2 ) dx dx d (ax 2 )
2 2  2 2 m 2 
d 2 eax d 2 2 2 d 2 eax d 2 2 2
= (2ax)eax = 2 aeax + 4 a 2 x 2 eax = (2ax)eax = 2 aeax + 4 a 2 x 2 eax
dx 2 dx dx 2 dx 1 2 2
= hω N 0e − x /2α Zero point energy
2
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Lecture 10 – Harmonic oscillator

Exercise Exercise

Calculate the mean displacement of the oscillator when it

is in a quantum state v. ∞ ∞
x = ∫ Ψ *v xΨ v dx = N v2 ∫ ( H v e − y
2 2
/2
) x( H v e − y /2
)dx
−∞ −∞

Hint: Use the recursion relation to expose vanishing ∞ dx

= N v2 ∫ ( H v e − y
2 2

integrals
/2
)α y ( H v e − y /2
) dy
−∞ dy
∞ 1
= α 2 N v2 ∫ H v2 ye − y dy
2
yH v = H v +1 + vH v −1
−∞ 2
H v +1 − 2 yH v + 2vH v −1 = 0
∞ 1  2
= α 2 N v2 ∫ H v  H v +1 + vH v −1  e − y dy = 0
−∞
2 
Orthogonality

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Permeation of Summary
wave functions
v
Probability in the
The solution of the Schrödinger equation for a harmonic
classically forbidden potential or the quantum-mechanical harmonic oscillator
region gets smaller
with increasing v
has the properties:
(quantum number). • The eigenfunctions are a Hermite polynomial times a Gaussian
Another Greater probability function.
correspondence near the turning • The eigenvalues are evenly spaced with the energy separation
principle result. points. Again of ħω and the zero-point energy of ½ħω.
correspondence to
• The greater probability near the turning points for higher values
classical case.
of v.
v

8 % of probability permeates into the

classically forbidden region.
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