CHM 112M: Lecture 4

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Arnab Ghosh
August 23, 2023

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1 Particle in a Box
We will first apply TISE to a 1D system to highlight the key aspects of QM. Our
main goal is to demonstrate how wave functions of simple systems can be ob-

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tained by solving SE. Furthermore, we aim to emphasize that quantum numbers
in QM arise as mathematical necessities and not by arbitrary assumptions1 .

2 Particle in 1D box
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Let us consider a particle of mass m in a 1D potential well of length a along the
x-direction as shown in Fig. 1. The potential is of the form

∞, for x ≥ a

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V (x) = ∞, for x ≤ 0 (1)


0, for 0 < x < a,


1 Note: This is Brief Overview of Class Topics (For Internal Use): Not a Lecture Substitute.
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E
N
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V(x) = ∞ V(x) = 0 V(x) = ∞

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x=0 x=a x

Figure 1: Schematic potential of 1D box.

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 which implies that the particle can’t exist at either x ≤ 0 or x ≥ a. The TISE
for the system can then be written as

h̄2 d2
− ψ(x) = Eψ(x), (2)

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2m dx2
by setting V (x) = 0 for 0 < x < a, where ψ(x) is the wave function associated
with the particle with energy E. This problem is so simple that it is possible to
guess the nature of the solution. One would expect that ψ(x) would be either
sine or cosine function. However, ψ(x) must be zero at the boundary x = 0 and
x = a since the particle can’t exist beyond 0 < x < a. Therefore ψ(x) can’t be
cosine function, rather a sine function of the form sin(πx/a), which satisfies the

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boundary condition (BC). More generally, sin(nπ) = 0, so the acceptable wave
function (labelled by index n) can be written in the form of
 nπx 

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ψn (x) = A sin , n = 1, 2, 3, ... (3)
a
where the normalization constant A is yet to be determined. Note that n = 0
is not allowed. This is because, for n = 0, both ψ and ψ ∗Rψ have zero values for
a
all x, which would imply that normalization condition ( 0 ψ 2 (x)dx = 1) is not
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satisfied. Substituting the above equation for ψ(x) in Eq. (2), we get

h̄2 d2  h̄2
 2 2
nπx  n π  nπx   nπx 
− A sin = − − A sin = EA sin , (4)
2m dx2 a 2m a2 a a
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which gives the expression for the quantized energy E (labelled by the same
index n, called the quantum number) of the particle as

n2 h2
En = n = 1, 2, 3, ... (5)
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8ma2
To evaluate A, we make use of the normalization condition, i.e,
Z x=a Z x=a  nπx 
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|ψ(x)|2 dx = |A|2 sin2 dx = 1, (6)

x=0 x=0 a

which yields r
2 iφ
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A= e , (set φ = 0 for convenience) (7)

a
apart from any arbitrary global (overall) phase factor. Plots of the wave func-
tion, energy and the probability density are presented in Fig. 2.
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Verify: The nature of the wave function and probability density are in-
dependent of the region in which the particle is confined. For example, if the
confinement becomes −a/2 < x < a/2 instead of 0 < x < a, we would get cosine
(sine) function for even (odd) ψ(x), but the plots in Fig. 2 would be identical
except for a shift in the x-coordinate.

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Figure 2: Energy levels, wave function ψ(x) and probability density ψ 2 (x) for
a particle in a one-dimensional box. Adapted from PKG’s book.
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3 Particle in 3D box
The treatment can be easily extended to a 3D box. Let consider, the particle
is confined in 3D box of dimension x = a, y = b and z = c, with one corner at
the origin [Fig. 3]. The PE is V = 0 inside the box and V = ∞ outside the box
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and on the walls. The SE for the particle in a 3D-box can be written as

h̄2
 2
∂2 ∂2

∂
− + 2 + 2 ψ(x, y, z) = Eψ(x, y, z). (8)
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2m ∂x2 ∂y ∂z

Since the motions along three orthogonal directions are independent of each
other, we can use separation of variables, i.e., ψ(x, y, z) can be written as product
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of three functions ψ(x, y, z) = φx (x)φy (y)φz (z). Substituting this in Eq. (8),
and dividing throughout by φx (x)φy (y)φz (z), we get

h̄2 1 d2 φx (x) h̄2 1 d2 φy (y) h̄2 1 d2 φz (z)

− − − = E. (9)
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2m φx (x) dx2 2m φy (y) dy 2 2m φz (z) dz 2

Three terms in LHS are identical in form, depends only on x, y and z respec-
tively, and the sum of the terms are constant. Mathematically this is possible
iff each term is equal to a constant. Writing E = Ex + Ey + Ez , Eq. (9) can
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be separated into three equations of the 1D type [Eq. (2)], each depending only
on one of the coordinates x, y or z. The solutions for the wave functions and

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 z

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V=0
inside the box

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b y

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a
x V = ∞ : outside and at the boundaries
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Figure 3: Schematic potential of a 3D box.

energies can then be written in a straightforward manner

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r
h̄2 d2 φx (x) 2  n πx 
x n2x h2
− = Ex φ x (x); φ n x (x) = sin ; En x = (10)
2m dx2 a a 8ma2
n2y h2
2 2
r
h̄ d φy (y) 2 ny πy
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− = E y φ y (y); φ n y
(y) = sin ; E n y
= (11)
2m dy 2 b b 8mb2
2 2
r
h̄ d φz (z) 2  n πz 
z n2 h2
− 2
= Ez φz (z); φnz (z) = sin ; Enz = z 2 . (12)
2m dz c c 8mc
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So, the total wave function and energy will be

r
8  n πx   n πy   n πz 
x y z
ψnx ,ny .nz (x, y, z) = sin sin sin , (13)
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abc a b c
!
h2 n2x n2y n2
Enx ,ny .nz = Enx + Eny + Enz = 2
+ 2 + 2z . (14)
8m a b c
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Note that we have now three quantum numbers to designate the state of the
quantum particle in 3D box and its respective energy. For a cubic box (a = b =
c), we have

h2
n2x + n2y + n2z .


E= 2
(15)
8ma

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 Here the lowest energy state is the one with nx = 1, ny = 1 and nz = 1,
termed the ground state, and denoted as (1,1,1). First excited state, is the
one with one quantum number is 2, and others are 1. So, there are three
such alternatives: (2, 1, 1), (1, 2, 1), and (1, 1, 2) — all have the same energy,

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but have the different wave functions. States with different wave functions but
same energies, are called “degenerate states”. This phenomena is known as
degeneracy and the number of such states for a given energy level is called the
“degree of degeneracy”. For the above example, three of the above states form
a three-fold degenerate states.
Remarks: Try to work out the particle in 2D box and verify that there is
trivial degeneracy for a 2D square box. Most cases, degeneracy is an outcome of

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geometrical symmetry, appears only in higher dimensions and not in 1D bound
state systems. For, the 2D case, the degeneracy is apparently lost (lifted) if we
break the square symmetry by making Lx 6= Ly (rectangular box) and thereby
making x and y directions non-interchangeable. However, even for rectangular

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box certain conditions can lead to degeneracies. For example, if Lx = L and
Ly = 2L, show that the E1,4 and E2,2 will have same energy. Such degeneracies,
which depends on the “accidents” of finding a certain numerical condition (here,
Lx = L and Ly = 2L), are called “accidental or numerical degeneracy”. Even
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for 2D square box, there could be additional or extra numerical degeneracy if
2 2
two set of positive integers satisfy the condition n21 + n22 = n01 + n01 2 . It should
noted that wave functions of excited states in 1D, have nodal points (simply
nodes), while, excited state wave functions of 2D have nodal lines and in 3D,
they have nodal planes. In 2D square box, verify that ψ2,3 (x, y) vanishes on the
line x = L/2 and on the lines y = L/3 and 2L/3. The concept of nodal planes
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will be discussed in connection with 3D hydrogen atom wave functions.

Applications: 1D or 3D particle in a box problem can be applied to a real
systems if idealizations are made. For examples, 1D box can be applied to a
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free electron in a wire or to free electrons in organic molecules with conjugated

chain. Similarly, higher dimensional box can be realized with nano-confined
geometries. Another application of 3D box problem can be used to estimate
translation energy levels of molecules.
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4 Hydrogenic Systems
System consisting of a central positively charged nucleus (+Ze) and one ex-
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tranuclear electron, interacting via a Coulomb interaction, is called hydrogenic

system. TISE for such a two-particle system can be written as

h̄2 h̄2
 2
∂2 ∂2
 2
∂2 ∂2
   
∂ ∂
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− + 2 + 2 − + 2 + 2 + V (xN , yN , zN , xe , ye , ze )
2mN ∂x2N ∂yN ∂zN 2me ∂x2e ∂ye ∂ze
ΨT (xN , yN , zN , xe , ye , ze ) = ET ΨT (xN , yN , zN , xe , ye , ze ), (16)
2 Look up Brahmagupta-Fibonacci identity.

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 In terms of the center of mass for the electron-nucleus system
mN xN + me xe mN yN + me ye mN zN + me ze
X= , Y = , Z= (17)
mN + me mN + me mN + me

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and relative coordinate of the electron w.r.t. the nucleus,

x = xN − xe , y = yN − ye , z = zN − ze (18)

one can write Eq. (16) as (Try)

h̄2 h̄2
 2
∂2 ∂2
 2
∂2 ∂2
   
∂ ∂
− + + − + 2 + 2 + V (x, y, z)

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2(mN + me ) ∂X 2 ∂Y 2 ∂Z 2 2µ ∂x2 ∂y ∂z
ΨT (x, y, z, X, Y, Z) = ET ΨT (x, y, z, X, Y, Z), (19)

where µ = mN me /(mN + me ) is the reduced mass of the electron.

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Since, the PE only depends on the relative distance, we can implement the
separation of variables

ΨT (x, y, z, X, Y, Z) = ψ(x, y, z)φ(X, Y, Z), (20)

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which upon substituting in Eq. (19) and dividing the same by ΨT (x, y, z, X, Y, Z) =
ψ(x, y, z)φ(X, Y, Z), yields

h̄2
 2
∂2 ∂2
 
1 ∂
− + + φ(X, Y, Z)
2(mN + me ) φ(X, Y, Z) ∂X 2 ∂Y 2 ∂Z 2
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h̄2 ∂2 ∂2 ∂2
  
1
− + + ψ(x, y, z) + V (x, y, z) = ET .
2µ ψ(x, y, z) ∂x2 ∂y 2 ∂z 2
(21)
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The above equation is true if each term is equal to a constant, i,e,

h̄2
 2
∂2 ∂2
 
∂
− + + φ(X, Y, Z) = φ(X, Y, Z) (22)
2(mN + me ) ∂X 2 ∂Y 2 ∂Z 2
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h̄2 ∂2 ∂2 ∂2
   
− + 2 + 2 + V (x, y, z) ψ(x, y, z) = Eψ(x, y, z), (23)
2µ ∂x2 ∂y ∂z
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satisfying ET =  + E. Eq. (22) represents center of mass motion of the two-

particle system in a potential free (V = 0) 3D space. Solution of Eq. (22) leads
to translational energies  of the system and the corresponding wave function
φ. Note that such free particle motions don’t have bound state solutions, hence
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can’t have a normalized wave function. Eq. (23) represents the TISE for the
relative motion of the electron w.r.t the nucleus in a potential field V (x, y, z). To
understand the electronic structure and energy states of the hydrogenic systems,
we need to solve this equation.
Reference:
1. Atomic Electronic Structure by P. K. Ghosh and P. K. Shukla. (PKG)