ffect, we have a repulsive As webarrier mentioned of infinite before, strength

the Schrödinger at eachequation end of contains th

where " is a function of x {["(x)]}. We can rearrange this equation to give
Thus the particle isoperator
trappedĤ.inInathis one-dimensional
case, since the potential box with impene-
d cenergy 2mE is zero inside the
Particle in a Box model
2
52 c
ls (▼ Fig. 12.13). only energy possible is the kinetic energy ofdx the particle U as it moves b 2 2

e mentioned before, forth along

the the x axis. equation
Schrödinger
Figure 12.13
The operator for thisthe
contains kineticenergy energy is
• Consider a particle with mass m that is free to
A schematic representation of a par-
Ĥ. Inmove
thisback
case, since theticleone
potential
in a one-dimensional box
and forth alonginfinitely dimension
energy
high potential walls.
with is zero inside U2 dthe 2 box, the
y possible is values
the kinetic 2 moves
between the x = 0 andenergy
x = L. of the particle as it 2m dx2 back and
g the x axis. The operator for this kinetic energy is V(x) = ∞ V(x) = 0 V(x) = ∞

Energy
• The potential energywhere is particle
V(x) of"the Planck’s constant divided by 2!, m is the mass of the part
is zero
2 2
d2/dx
at all points along its is the
U atsecond
path,2 except d
the derivative with respect to x. Thex form of this
endpoints x = 0 andcomes 2
from
x = L, where the
V(x) isdescription
2 of waves in classical physics. Inserting th
2m dx
infinitely large. tor into the Schrödinger equation Ĥ" x=0
! E" gives x=L

Planck’s constant divided by 2!, m is the mass 2of the 2 particle, and
• Schrödinger equation contains the energy operator Ĥ. U d c
he second derivative with respect to x. The 2form of2 this 5 Ecoperator
2m dx
Copyright 2017 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or
Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restr

m •the description of waves in classical physics. Inserting

The potential energy is zero inside the box, the only energy possible is thethis opera-
kinetic energy of the
e Schrödinger where
equation
particle as it moves is a!along
"Ĥ"
back and forth function x of
gives
E" the x {["(x)]}. We can rearrange this equation to
axis.
81982_ch12_0436-0497j.indd 456

U dc 2 2 d2 c 2mE
2 5 Ec à 2 5 2 2 c
dx U
2m dx2
 Particle in a Box model
goal is to find specific functions !(x) that satisfy this equation. No-
the solutions to this equation are functions such that d2!/dx2 !
)!. That is, each solution must be a function whose second deriva-
• Each
he same formsolution must be function.
as the original a functionOne
whose secondthat
function derivative
behaveshas the same form as the original
this
function. For example, consider the function A sin(kx), where
e sine function.
• One function
are constants. We willthat
nowbehaves thissecond
take the way isderivative
the sine function.
of this function
ect to x:
d2 d d sin kx d
1 A sin kx 2 5 A a b 5 A 1k cos kx2
dx2 dx dx dx
d cos kx
5 Aka b 5 Ak 12k sin kx2
dx
5 2Ak2 sin kx 5 2k2A sin kx
have shown that
d2 1A sin kx2
2 5 2k2 1A sin kx2
dx
is just the type of function that will satisfy the Schrödinger equation
article in a box. In fact, when we compare the general form of the
ger equation
 ! 2 æç ¶ 2 ψ ö÷
- = Eψ
2m çè ¶x 2 ÷ø

• This is a second order differential equation – with general solutions of the form:
y = A sin kx + B cos kx

æ ¶ 2ψ ö
ç ÷ = -k 2 (A sin kx + B cos kx ) = -k 2 ψ
ç ¶x 2 ÷
è ø

• SE Þ
-
! 2 æç ¶ 2 ψ ö÷ æç ! 2 ö÷
= -
2m çè ¶x 2 ÷ø çè 2m ÷ø
(
× - k 2
)ψ = Eψ

Þ
k 2! 2 (i.e. E depends on k).
E=
2m
Restrictions on y

• In principle Schrödinger Eqn. has an infinite number of solutions.

• So far we have general solutions:

– any value of {A, B, k} ® any value of {y,E}.

• BUT – due to the Born interpretation of y, only certain values of y are physically acceptable:

– outside box (x<0, x>L) V = ¥ Þ impossible for particle

to be outside the box
\ ½y½2 = 0 Þ y = 0 outside box.

– y must be a continuous function

Þ Boundary Conditions y = 0 at x = 0
y = 0 at x = L.
Effect of Boundary Conditions

1. x = 0 y = A sin kx + B cos kx = B
0 1
y=0 \B=0
Þ y = A sin kx for all x

2. x = L y = A sin kL = 0

A=0 ? O sin kL = 0 ? P
(or y = 0 for all x)

sin kL = 0 Þ kL = np n = 1, 2, 3, …
(n ¹ 0, or y = 0 for all x)
 uss in more
L must be 1.detail
We below, this means
sum these that theover
probabilities squarebeof
Tothe theprecise,
length
more wave
of thefunc-
thebox
probability of finding the particle on a s
xuated
! 0 toatxa!given
L) bypoint gives the
integration relative
from x ! 0probability L: of length
to x x!axis finding dxasurrounding
par- point x is !2(x) dx. Because the
r that point. Wavefunctions
Allowed This concept and is relevant
Energiesto Lthe boundary conditions
ticle in the box, the sum forof all those probabilities along the x ax
cle in a Total
box because the total
probability probability in2 a to
of finding given L must
x ! state be 1.beWe
must 1. sum these probabilities over the lengt
5 3 c 1x2(fromdx 5x 1 0 to x !ofL)theby integration from x ! 0 to x ! L:
ore precise,
the the probability
particle of finding the
in the box 0
particle on a !segment
• kdx
length is surrounding
restricted to a point
discretex set
is !of2(x)
values: k = np/Lthere is one par-
dx. Because L
Total probability of finding
uting !(x)
he box, the!sumA sin[(n"/L)x], we have
of all those probabilities along the x axis from x ! 0 5 3 c2 1x2 dx 5 1
the particle in the box 0
L must be 1. We L sum these probabilities
L over the length of the box
• Allowed wavefunctions:
! 0 to x ! L) c2integration A2 sin
yannp
x2!
pL:
= A sin(nSubstituting
x/L)
1 !(x) ! A sin[(n"/L)x], we have
3 by 1x2 dx 5 3 from 0 toxbdx
x !5
0 0 L L L
L 2 2 2 np
Total probability
of finding
L 3 c 1x2 dx 5 3 A sin a xbdx 5 1
2 np 5 3 c12 1x2 dx 5 1 0 0 L
the particle in3thesin a xbdx 50 2
box L A L
0
2 np 1
ting !(x) ! A sin[(n"/L)x], we have or 3 sin a xbdx 5
ue of the integral is L/2, which means that 0 L A2
L L
c2 L
1 x 2 dx 15 A 2
sin 2 np
xbdx 25The
1
value of the integral is L/2, which means that
3 5 2 3 and a A
0 2 A 0 L 5 ÅL L 1 2
5 and A5
L 2 A2 ÅL
2 np 1
3 sin a xbdx 5
0 L A2 æ npx ö
• Normalization: A = Ö(2/L) Þ ψn = 2
L
sin ç ÷
e of the integral is L/2, which means that è L ø
ed, or duplicated, in whole or in part.
2017 Due to electronic rights, some third May
partynot
content mayscanned,
be suppressed frominthe eBook
or inand/or eChapter(s).
verall learning experience. L
Copyright
Cengage 1
Cengage
has Learning
Learning. All
reserves
Rights
the right
Reserved.
to remove 2
be copied,
additional
materiallycontent
or duplicated,
affect theatoverall
any time
whole
if subsequent
experience. rights
part. Due to electronic rights, some third party content may be suppres
restrictions requiretheit.right to remove additional content at any tim
Editorial review
5 deemed that
and
any suppressed content
A5
does not learning Cengage Learning reserves
Allowed Wavefunctions and Energies

æ npx ö
• Normalization: A = Ö(2/L) Þ ψn = 2
L
sin ç ÷
è L ø

k 2! 2 n 2 π 2! 2
• Allowed energies: En = =
2m 2mL2

n 2h2
Þ En =
8mL2
equation, where each function corresponds to a given energy state:

n Function Energy
The application of the boundary conditions has led to a series
2
2 p h of quantized energy levels. That is, only certain energies are
1 c1 5 sina xb E1 5
ÅL L 8mL2 allowed for the particle bound in the box.
2 2p 4h2 h2
2 c2 5 sina xb E2 5 5
ÅL L 8mL2 2mL2
2
2 3p 9h
3 c3 5 sina 460
xb Chapter
E 5 12
3
Quantum Mechanics and Atomic Theory
ÅL L 8mL2
2 4pFigure 12.14 16h2 2h2 10 !"L2 2
4 c4 5 sina (a)
xbThe first Ethree
4 5 energy 5
levels for2a L
ÅL 8mL2 box
Lparticle in a one-dimensional mLin E3
9 ψ3 ψ 32
Y Y increments of h2/(8mL2).Y(b) The wave
functions for the first three levels plot- 8
ted as a function of x. Note that the
maximum value is "2 /L in each case. 7
Notice something very important about these
(c) The square of the wave functions results. The application of
the boundary conditionsforhas led three
the first to a levels
series of quantized
plotted as a energy levels. That is,
6
function of x. Note that the maximum 2
only certain energies are allowed for the particle bound in the 5 box. This result !" 2 L
value is 2/L in each case. L
fits very nicely with the experimental evidence, such as the hydrogen E2 emission
4 ψ2 ψ 22
spectrum, that nature does not allow continuous energy levels for bound sys-
tems, as classical physics had led us to expect. Note that the3energies are quan-
tized, because the boundary conditions require that n assume only integer
2
values. Consequently, we call n the quantum number for this system.
!"L2 2
L
E1 ψ1
We can diagram the solutions to the particle-in-a-box 1 problem conve- ψ 12
niently by showing a plot of the wave function that corresponds
0 to each energy
level. The energy level, wave function, and probability distribution are shown 0 x L 0 x L
(a) (b) (c)
Quantum Numbers

• There is a discrete energy state (En), corresponding to a discrete

wavefunction (yn), for each integer value of n.

• Quantization – occurs due to boundary conditions and requirement

for y to be physically reasonable (Born interpretation).

• n is a Quantum Number – labels each allowed state (yn) of the

system and determines its energy (En).

• Knowing n, we can calculate yn and En.

 n 2h2
Energies En =
8mL2

• En µ n2/L2 Þ En­ as n­ (more nodes in yn)

En­ as L¯ (shorter box)
n­ (or L¯) Þ curvature of yn­
Þ KE­ Þ En ­

E y E
2 node

Nodes in the wavefunction – points at which yn = 0

(excluding the ends which are constrained to be L¯
zero).
y1
Number of nodes = (n-1) y1 ® 0; y2 ® 1;

L1 L2
• En µ n2 Þ energy levels get further apart as n­
n E

9h 2
3 E3 =
8mL2

4h 2
2 E2 =
8mL2

h2
1 E1 = h2
8mL 2 ZPE =
0 8mL2

• Zero-Point Energy (ZPE) – lowest energy of particle in box:

h2
ZPE = E min = E 1 =
8mL2
• CM Emin = 0
• QM E = 0 corresponds to y = 0 everywhere (forbidden).
Density Distribution of the Particle in the 1-D Box

• The probability of finding the particle between x and x+dx (in the state represented by
yn) is:
Pn(x) = |yn(x)|460
2 dx = (y
n(x)) dx (yn is real)
Chapter 12 2 Quantum Mechanics and Atomic Theory

Figure 12.14
æ npx ö !"L2
10 2

Pn (x ) =
(a) The first L
2 2 three energy levels for a
Þ sin ç ÷dx
particle in a one-dimensional box in
L 9
E3
ψ3 ψ 32
è L ø
increments of h2/(8mL2). (b) The wave
functions for the first three levels plot- 8
ted as a function of x. Note that the
maximum value is "2 /L in each case. 7
(c) The square of the wave functions
for the first three levels plotted as a 6
• Note: probability is not uniform
function of x. Note that the maximum 2
value is 2/L in each case.
5 !" 2
L
L

– yn2 = 0 at walls (x = 0, L) for all yn. 4

E2
ψ2 ψ 22

– yn2 = 0 at nodes (where yn = 0). 3

2 !"L2 2
L
E1 ψ1
1 ψ 12

0
0 x L 0 x L
(a) (b) (c)
 the general expression for energy:
n2 h 2
E5
Assume that an electron is confined to a one-dimensional8mL
box
1.50 nm in length. Calculate the lowest three energy
2

levels for this electron, andThe

calculate theelectron
mass of an wavelength of light
(m) is 9.11 necessary
" 10#31 to promote
kg; the dimension of the the
boxelectron from the ground state
to the first excited state. (L) is 1.50 nm, or 1.50 " 10 m; and the value of Planck’s constant is
#9

6.626 " 10#34 J s.

For n ! 1 we get
112 2 16.626 3 10234 J s2 2
E1 5 5 2.68 3 10220 J
182 19.11 3 10231 kg2 11.50 3 1029 m2 2

Copyright 2017 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s).
orial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.

h12_0436-0497j.indd 460 9/18/15 1:52 PM

Particle in a 2-D Square or 3-D Cubic Box
• Similar to 1-D case, but y ® y(x,y) or y(x,y,z).
• Solutions are now defined by 2 or 3 quantum numbers
e.g. [yn,m, En,m]; [yn,m,l, En,m,l].
• Wavefunctions can be represented as contour plots in 2-D