Peter Atkins • Julio de Paula

Atkins’ Physical Chemistry

Eighth Edition

Chapter 9
Quantum Theory:
Techniques and Applications

Copyright © 2006 by Peter Atkins and Julio de Paula

 Chap 9
Quantum Theory: Techniques and
Applications
Objectives:

Solve the Schrodinger equation for:

• Translational motion (Particle in a box)

• Vibrational motion (Harmonic and anharmonic
oscillator)
• Rotational motion (Particle on a ring & on a sphere)
Fig 9.1 Particle in a one-dimensional box

• Particle is not free

• ∴ For acceptable ψ,
boundary conditions
must be set:

• ψ must vanish
at x = 0 and x = L

• Implies quantization!
 Fig 9.2 Allowed energy levels for a particle
in a one-dimensional box
Normalized wavefunction:
Ψn (x)  
2 1/2
L
 
sin nπx
L

n 2h 2
En  2
n = 1, 2, 3, …
8mL (bilangan kuantum)
n ≠ 0 so: h2
E1 
8mL2
is called the zero-point energy

dan

ħ =h/2
Contoh Soal:
1. Partikel dengan massa 2x10-26 g diemisikan dalam kotak 1D
dengan panjang 4 nm. Tentukan frekuensi foton yang diemisikan
ketika partikel pindah dari n=3 ke n=2.
(h=6.626x10-34 J.s)

Jawab:

hv=Eupper-Elower=nu2h2/8ml2-nl2h2/8ml2

2. Elektron keadaan stasioner dalam kotak 1D dengan panjang

kotak 0.3 nm mengemisikan foton pada frekuensi 5.05x1015 s-1.
tentukan bilangan kuantum awal dan akhir dari transisi ini. Massa
elekton=9.109x10-31 kg
Fig 9.3 First five normalized wavefunctions of PIB

0 L
Fig 9.4 First two normalized wavefunctions of PIB
with probability distributions
 Real world PIB: a delocalized π electron
in a conjugated system

1 β-Carotene

Suppose we can treat the  electrons of a long polyene, such as b-

carotene (1), as a collection of electrons in a box of length 2.94 nm.
Then for an electron to be excited from the level with n = 11 to the
next higher level requires light of frequency?
Correspondence Principle:

• Classical mechanics emerges from quantum

mechanics as high quantum numbers are reached

• i.e., particle may be found anywhere as n → ∞

Fig 9.5 Probability of two wavefunctions

ψ1 and ψ3 are
orthogonal  Ψ1* Ψ3 dτ  0

or In Bra-ket notation:
orthonormal n n'
〈1|3〉 = 0 when n ≠ n'
Ortogonalitas :
Ψn (x)  
2 1/2
L
sin nπx
L
 

Sin nit*Sin njt=1/2 cos[(ni-nj)t]-1/2 cos [(ni+nj)t]

Motion in two and more dimensions

Pemisahan Variabel:
Penyelesaian untuk setiap arah (X dan Y)

Karena :
Fig 9.7 Contours for particle in 2-D rectangular well

n1 = n2 =1 n1 = 1, n2 =2 n1 = 2, n2 =1 n1 = 2, n2 =2
Motion in 3 dimensions
Fig 9.8 Contours for particle in 2-D square surface

Here, L1 = L2 = L
n1πx n2 πx
Ψn1 ,n2 (x, y)  2
L
sin L
sin L

h2
En1n2  (n12  n22 )
8mL2
Ψ1,2 and Ψ2,1

are said to be degenerate

 Three-dimensional nanocrystals of
semiconducting materials containing
10 to 105 atoms are called quantum
dots

https://www.youtube.com/watch?v=0EokkhdppgE
 Penetration into and through barriers
Tunnelling : Leakage by penetration through a classically
forbidden region

0 L
Fig 9.9 Tunnelling of a particle through
wall when V < ∞
B”=0 (refleksikan):
reflection probability( )
Contoh:
 An STM image of cesium
atoms on a gallium
arsenide surface.

Visualization of the reaction SiH3 → SiH2 + H on a 4.7 nm × 4.7 nm area of a

Si(001) surface. (a) The Si(001) surface before exposure to Si2H6(g). (b)
Adsorbed Si2H6 dissociates into SiH2(surface), (c) After 8 min, SiH3(surface)
dissociates to SiH (surface) and H(surface)
Fig 9.13 Wavefunction of a heavy particle decays more
rapidly than that of a light particle

• Light particles have

higher probability of
tunnelling
 Tunneling
Chemical effects of tunneling:

• Isotope-dependence of reactions rates

• Transfer of a proton in an acid-base reaction

• Mechanism of enzyme-catalyzed reactions

• Electron transfer in redox reactions

• Scanning tunneling microscopy (STM)

Fig 9.16 Tip of a Scanning Tunnelling Microscope (STM)

Pt-Rh or W

Ultrahigh
vacuum
 Title : The Making of the Circular Corral
Media : Iron on Copper (111)

We can predict what goes on in the corral by solving the classic eigenvalue
problem in quantum mechanics -- a particle in a hard-wall circular box.
 Title : Stadium Corral
Media : Iron on Copper (111)