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13 views29 pagesQuantum Mechanics 1
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/ 29
QUANTUM MECHANICS-I
CHAPTER
In the previous chapter we have seen how the classical concepts cannot explain the behaviour of
microparticles. It was observed that the failures of classical mechanics are intimately associated with
two gencral type of effects : (i) the wave character of the particle and (ii) the probabilistic nautre of
‘our observations. Therefore, in order to describe the behaviour of microparticles we must have a
different physical theory, called quantum mechanics or wave mechanics.
In this chapter we would at first like to obtain a wave equation for a one-particle system. The
solutions of this equation for some simple problems will be used to interpret the properties of
microsystems in terms of their wave properti sequently a more general mathematically
rigorous, nonclassical, postulatory approach will be introduced in the next chapter to obtain the basic
Jaws governing the behaviour of microsystems. While the behaviour of macroparticles is described by
the Newton's laws of motion, the behaviour of microparticles will be described by the laws of quantum
mechanics. The validity of these laws for different problems are then justified by the fact that the
solutions of the equations agree with the experimental results. Before examining the equations, we
first start by discussing briefly the mathematical aspects of wave phenomena.
2.1 MATHEMATICAL DESCRIPTION OF WAVES
Let us consider a wave progressing along the X-axis as shown in Fig, 2.1. This is called a
progressive wave. This wave motion and all other types of wave motions can be described
quantitatively by the differential cquation
Sp _ 1 (dX o
‘The value y is the amplitude function and is_a measure of the variation of displacement along
the Y-axis at a particular distance x along the X-axis, c is the velocity with which the wave is travelling
and {is the time. This is a second-order differential equation with a constant coefficient and hence it
isa lincar differential equation. This differential equation has many solutions. One of these solutions
in terms of the sinc function is
p = Asin 21 (X/A = 1) (22)
where A is the wavelength, v is the frequency and A is the amplitude, If two waves y, and py cross
each other, then the resultant amplitude is the sum of the amplitudes of each separate wave at the
point of crossing. Mathematically, it can be stated that the resultant amplitude function y is equal to
the linear combinations of two separate amplitude Functions yy and yw, .
Pm ayy, + ayy ~23) Quantum Chemistry
32
i, ample of the principle of
where a, and a3 are two arbitrary constants. This equation 'S ea of the wave equation
Superposition. According to this principle any linear combination of cular orbital theory.
(2.1), is also a solution. This principle is useful in the study of mole’ to right. An equivalent wave,
Equation (2.2) represents a plane wave travelling from left 10
travelling in the opposite direction, is given by
gp =A sin 20 (&/A + vt) . ite direct
when two waves of the form of Eq, (2.2) travel with equal speed but in opposit
resultant amplitude by the principle of superposition will be
p =A sin 2x (@/2 — 1) +A sin 2x @/A +) (24)
= 2A sin 2.x/A cos 20 vt
the new resultant wave, which docs not move
either forward or backward, is known as a
standing wave or a stationary wave.
Mathematically, all waves whose amplitude
function can be factorised into a factor indepen-
dent of space coordinates and a factor
independent of time, are called standing waves
(Fig. 2.1). Empirically, it is found that the
behaviour of an electron in an atom can be best
described by considering standing waves.
From Eq. (2.4), it is obvious that y
vanishes irrespective of the value of ¢, for the
points at which sin 27x/A = 0 ic, at x
= 0,/2, 22/2...nA/2. These points are known .
as nodes (minimum amplitude). The distance between two successive nodes is 4/2 and midway
between two nodes are the positions of maximum amplitude, or antinodes.
2.2 THE SCHRODINGER TIME-INDEPENDENT WAVE EQUATION
In 1926, Schrodinger proposed a differential equation for relating the energy of a microsystem to its
space coordinates. For a particle of mass m moving in one-dimension with energy E, this is given by
tions, then their
Fig. 2.1 Standing harmonic wave.
2 2,
TY , Me _ yey =0
aa i ¢ OY
where y is a function of x and is called a wavefunction and the factor V(x) is the potential energy of
the particle at a point x. This equation cannot be proved or derived. Rather it can be taken as the
starting point for a discussion of modern quantum theory, It is possible, however, to make an
argument for the Schrodinger equation in the following way. :
Let us consider an electron wave moving along the X-axis and behaving lik : athe
amplitude function for this wave from Eq, (24) can be written as Ske a. staneing Wave.
# 1) = 2A sin 2784/0 .cos2mt =v () F (0) = Ye) cos2mt (25)
where y (x) isan abbreviation for 24 sin 2ax/2 and is function of: coordinates only and f(t) is 82
sporevtation for cos 2z0vt, and is afunction oft coordinate only i te¥'only’a
aeonch other. Simple differentiation of Eq, (2.5) then gives.” PeS° 0 functions are independent
&— Pyle)
= cos 20vt,
ae
ae
5
FP = - ve). 200 sin 2a Quantum Mechanics-1
3B
3,
xe = = v@) 40° cos 201
Substituting these values in Eq. (2.1) we get
&
0s 2avt VE) _ Lee) 422,205 2000
a? 2
Pv) 1
or VO) 2 age
Jac y(e) (26)
This is a wave equation, similar to E i i i
T 7 'q. (2.1), except that this equation specially relates to a
standing wave and has the variable ¢ eliminated from it. ”
Since c = Av, Eq, (2.6) becomes, ot =- Sue) (21)
Now, in order to aj
+ to apply this equation to microparticles, let us introduce the de Broglie equation
for matter waves, i.c.,
4—-*
ime
22a?
into Eq, (2.7), so that fe =- ore) (28)
In order to express this equation in terms of energy, we make use of the fact that the total energy (E)
is the sum of the kinetic energy (T) and the potential energy (V). Therefore, the kinctic energy (7) is
given by
T= 3m? =(E-V) or my? =2(E-Vm
2, 2
Substituting this value in Eq. (2.8), we obtain i + a st E-VYw=0 (29)
This is the famous Schrodinger equation for a single particle of massm moving in one dimension,
For three dimensions, it takes the form
2 2 2 2
Sy Sy oH Sem E_yyno (210)
ér by 62 hi
where y and V are functions of coordinates x, y, z and y is known as the wave function, The
Schrodinger equation for a one-particle system is generally written in the form
we [e@.&. & en a
~aa aa ta t a Vt Ve rEy wn(2)
822m |or dy? dz?
we have obtained the Schrodinger equation by fitting the de Broglie equation for wave-particle duality
into the classical wave equation. Since classical wave does not possess particle characteristics, such a
method of derivation of the Schrodinger equation is far from rigorous. This equation is independent
of time variable and is also known as the Schrodinger time-independent wave equation. We shall later
see that this equation appears as a postulate of quantum mechanics and may be taken as a starting
equation for discussing the behaviour of microsystems.
2.3 INTERPRETATION OF THE WAVE FUNCTION
‘The wave function is, by nature, asort of amplitude function. In classical mechanics the square
of wave amplitude, associated with the electromagnetic radiation, is proportional to the intensity of Quantum Chemistry
a
yor particle density,
f the intensit u dens
bara the uncertainty principle,
tion and momentum
tensity of light has
p is a mes
ef Ys nies is based on the
‘measure the posit
iele density or intensily
ed as proportional (0 the
bility of finding a particle
radiation, Hence the square of the absolute valu
However, our present accepted idea of y in quantum mee!
According to this principle, itis not possible to simultaneously
of a microparticle such as clectron, precisely. So, the idea of part
should be treat
no place in quantum mechanics, According ‘0 Bom, ||" sh ba
probability of finding a particle at a point at any given moment. Since the proba! sure of the probability
‘ata given point in space must be real, more generally, yy is taken 28 toe rhe complex conjugate f
of finding a particle at any point, ify is a complex function. The function 1S the cot a der a a ol
and their product will always be a real non-negative quantity. As am example, let us .
poatid : '
where’ = V7 . The square of this quantity will always be imaginary. The complex conjugate of y is
yp’ =a-ib
so that the product
y'v 0
alued, continuous ang
When x = 0 (v) is acceptable wave functio
nam 1 ©) pt e = 208 ge = 7A; exists.
Ser ae exists and (vi) is a acceptable as fx" (
0 0 1
© 2 oe
ute gee -2br exists,
When.x = 0 (vii) is acceptable since fe? dx = f e
oy .
But (viii) is not acceptable as = J e~ ** dx diverges.
(i) is not acceptable because though it is continuous at x =0 but its first derivative,
Lew 141 = ~ 67 IV isnot continuous atx = 0.
2.5 NORMALISED AND ORTHOGONAL FUNCTIONS
(a) Let us consider the Schrodinger equation (2.9). If y is a solution of this equation, N p is also
‘a solution of the equation, where N is any constant factor. Since y occurs in every term of the
Schrodinger cquation, the multiplication by a constant factor does not effect the equation and
wavefunction in anyway. This frecdom to vary y by a constant factor makes it possible to convert
proportionality sign in (2.12) into an cquality sign.
Pe |y Pdr =N*| p Pde = | Ny [de (214)
IfN = 1, then probability P = | y [dx and if N # 1, then P = | Ny [2dr
If | y [de ( = p"y dx) is equal to the probability of finding the particle in the infinitersimal
distance element dr, then sum of such probabilities must be unity This can be apeeed oe
f wy dc =1 (2.15)
When a wave function satisfies the above relation it is
WN 1, then y is not nomalised. Since N is an art
such a way that the total probability over the whole Space
normalised function. If the new function (N y) is to be ni
S said to be nonnalised function.
bitrary constant, we can choose its value it
¢ becomes unity, We assume that (NY) is?
‘ormalised it must meet the requirement
or
J (NPY y) de =
v2
de=1
or
(2.18) Quantum Mechanics-1 ra
where N is called the normatisation constant, From the value of integral (2.16) we can find N which
may be used to obtain the normalised functi p imensi 7
sanyo wee cans nction wy) . For three dimensional system, the condition
f wydt=1 [dv = volume clement]
= 12
and the normalisation constant N = 2
fv pat
‘The normalising condition (Eq. 2.15) implies that the particle is likely to be found in every region
ofagiven volume, whatever may be the location of the region in space, and the sum of the probabilities
of the particle in all the regions in space must be equal to 1. Obviously, for every wave function to
satisly Eq. (2.15), the particle must exist in space.
(b) If y; and y, are the two acceptable wavefunctions of a given system then these functions are
said to be mutually orthogonal if
231)
f wivjae=0 if fej (2.18)
For three dimensional system, it takes the form
Sv
The orthogonality conditon (Eq. 2.19) in terms of vector algebra means that the scalar product
of the function-vectors y;,¥; » vanishes. This is possible only if these vectors are completely
independent of one another. Likewise in quantum mechanics, orthogonal functions are completely
independent functions and one cannot be expressed in terms of others.
When y; and yj of a system satisfy the condition of orthogonality ie.
dt = 0,54) (2.19)
f vivjdt =O i#j and that of normalization i.e.
S vivjat
then these functions are said to be orthonormal implying that the functions are normalised and at the
same time also mutually orthogonal.
Example 2.3. Normalise the functions y= *
constant).
Let the normalised function be Nx’ . Therefore, by (2.15)
k
JL owe J ean or wf tant
0 0 0
u
2 over the interval OSx Sk (k isa 38
k
or nN, E]. =1 3
v2
2
Quanturn’ Chemistry
Hence the normalised function is (
Example 2.4. Show that y,=x and y,=x" are orthogonal over the interval
~ksx = J cosnxsinnx de
7, a
o o
a 2
a4 1m.
= af x0 (2 cos nx.sin nx) de > fg J sin ne de
1 | cos 2ne = 2 feos an — cos 0
bg po [ 2n | aan | 1
= gya-pe0
Hence the given functions are orthogonal.
2.6 SCHRODINGER TIME-DEPENDENT WAVE EQUATION
Let us consider back the general wave equation (2.1). Its gencral solution in exponential form is
given as ;
W (0) = Cexp [2ni (/A = o1)] = Ceoxp [2nix/A] exp | — 2niv] (2.20)
where Cis an arbitrary constant and and v are the wavelength and frequency respectively.
Substituting C exp [2tix/A] = y(x) in eq. (2.20) we get
Wx, 1) = Ye) exp [ ~ 2nivt]
where p(x) is the time-independent wavefunction.
(2.21) 40 Quantum Chemistry
Substituting v = g in eq, (2.21) we get
W@, t) = (x) exp [ — 20iEt/h] w(2.22)
Differentiating eq. (2.22) with respect tot we have
Meo C1) = (x) ( — 2niE/h) exp [ - 20iBt/h]
= me) Gs ‘2ni/h) exp [ - 2xiEt/h] (2.23)
Replacing Ey(x) by ol + Se Ve) JG) from eq, (2.9) in eq, (2.23) we obtain
=| -# “at ve G2) exp [ — 2iEt/h]
oa
te +t S+v0 ve) ( 2) exp [— 2iEt/h]
= © F vey |w (2.24)
=| -g ete | ve ae
This is the Schrodinger-time dependent wave equation. For three- demensional system it takes
the form
h_ AW (x,y, 2,0) chee Oe. 0s de
pene St 5+ S] + Vey. |Yeyze
2a or Bem (ae ay? az* G92) | ME ¥s200)
=HW(x,y,2,0)
ae #
where H= +S
Ee a aw
is called the Hamiltonian operator of a particle in a three-dimensional space.
Stationary States
In quantum mechanics, the state of a system is specified by the wave function W (x,y,z, ), which is
a function of both the space coordinates and the time coordinate, This function contains all the
information necessary for our purpose and is not directly measurable, in contrast to the classical concept.
Let us now consider the wavefunction W(x, ) of the form (2.22). The probability density
|W |? for such a wavefunction is
wy = { veyerneve ei playe ~ HEYA }
= {v" coves } femerheE”M} . This may be
explained as follows :
(0 Firstly, this is in accordance with the Heisenberg uncertainty principle, Ax Ap, = é. Ifwe
omentum becomes exactly zero. Under such condition, the
finite. But the particle is inside the box and the maximum
than the length, a of the box. Hence energy cannot be
consider energy E is zero, then mi
uncertainty in position becomes in|
uncertainty in position can never be greater
zero even at the lowest energy state.
(ii) Secondly, if E = 0, then” = 0 and consequently, y = 4 sin kx = 0 everywhere within the
box. This means the probability density | ¥ |? is also zero everywhere and there exists no state at all.
‘This goes against our initial assumption that the particle Ties inside the box. Hence E = 0 is not
acceptable.
Factors influencing the Energy
(a) Considering (2.40) we find the translational kinetic energy E,, decreases as the length a of
the box increases and asa + 0,E -» @. Quantum Chemisiy
"7 ‘ is
The energy difference between two successive energy levels
Qn + Ih? (2.42)
AEH Ens, a
This difference becomes negligibly small as @ bi
treated as a free particle whose energy is not quantize
the translational energy of an atom or a molecule is found to
of the box is not very small. . is the f
(b) The second factor that influences the energy or energy difference a ee
Particle. Thus, ifa small particle like an electron i confined in a box of the size of atomic of Molecular
dimension, the energy difference A E is appreciable ands quantized. But, for a partite of large mass
moving in'a space of comparatively large demension, the energy E or energy difference AE is
negligibly small to be detected. Hence such a particle will not have quantized energy value and will
behave like a free particle with continuous energy.
Normalisation of the Wavefunction
We have not yet determined the value of the arbitrary constant A of Eq. (2.39). Its value
is calculated by normalising the wavefunction y . The probability that the particle is somewhere
betweenx = O andx = ais unity because at all the times it is somewhere in.the box.
ticle may be the;
ecomes very large. The par e
‘d but continuous. Since his a small constan
be almost unquantised, when the length
Therefore, f Viv,de=J A sin? 2 ae =1
0 0
But sin? = F (1 — cos 2B
a2 @
« a @
+ agli alt _ i f 2am
0 0 0
_
‘2)2
A= () (2.43)
Thus, the normalised wavefunction of a particle in a one-dimensional box is given by
1
2)2 nme
Yn = Q) sin wu (2.44)
Orthogonality of the Wavefunctions
We have thus a whole set of wavefunctions, each corresponding to a particular value of ener;
and characterised by quantum number n, Let us now consiler wordietea each ea ed
yj corresponding to two different states ofa particle in a box. Then the integral
J vinsarn Jf) sn 2) (2) an (22
0 0 a .
a
Let m/a=" 5 de= (Ela
# = Owhenx = O ands = 2 whenx = Quantum Mechanics-I
5
: a
zl i 2 ,
Therefore, f Vivjde = 2) f sin (m4) .sin (nj14) du. ()
° 0
. , A 1
Since, sinnyse.sinnjy = Leos (nn) 4 — cos (1, +n) 1]
4 Ed Ed
* 2a1
f Pivjae =o02 f cos (n;—n) edu Hi cos (4; +n) udu
0 0
fl x
sin (1; — mH = Gy sim + oo]
jt nj i
; = (2.45)
[Since, sin max = 0, for integral values of m]
a
Thus, we have, f Vivjde=0; Te] =(2.46)
0
The wavefunction for different states of the system are thus orthogonal to each other and in
general, solutions of the Schrodinger equation for a system corresponding to different energy values
are always orthogonal. Both the normalised and the orthogonal character of a sct of wave function
can be combined by writing
Svjpjpae = oy (24)
where oy is called the kronecker delta and is defined by
64 = 0; when i # janddy = 1; wheni =j (2.48)
Obviously, the wavefunctions are orthonormal.
Probability of Finding the Particle
Classically the probability of finding a particle is the measure of the time spent by the particle
ata certain location, which, in turn, is the measure of the velocity of the particle, A classical particle
will travel from one end of the box to the other end with uniform velocity. Hence the probability of
finding a classical particle is uniform throughout the box.
Quantum mechanically, the probability of finding a particle P(x) over an infinitesimal distance
is given by
2 ae = (2) sin? 2.
P@)=|¥, Pae= BI sin? I ae
2 nse
P va
and the probability density | on (249)
= 2 sin
@
semum, sin? 2% ‘jn ;
For this probability density to be maximum, sin’ “== must be equal to 1. This is possible only if
pea ed te
sin? 2 = sin? (n +2, mW =01,2
or nox Qvt), saa (22)
a 2 an OY
6 Quantum Chemise
sete. P(e) is maximum (250)
n
oe ,
Hence for a state n = 1, the most probable position of the particle is 2 because next higher
Positions are outside the box.
Similarly using (2.50) we have for
‘ti a4 3a
n = 2 the most probable positions are atx = 4°4
3a Sa
n = 3 the most probable positions are atx = 7 erie:
a: a 3a Sa Ta
‘n= 4 the most probable positions are atx = Fy + "+g
All other positions are outside the box.
Dimension of the Wavefunctions
Probability is a dimensionless quantity by definition. Therefore, the quantity «| y |? dx is
dimensionless but dr has a dimension of length. Hence the dimension of a normalised wavefunction
¥ (x) is (length)~”, Similarly, for two-and three-dimensional systems, the dimensions of the
wavefunction y (x, y) and y (x, y,z) must be (length)! and (length)? respectively.
Example 2.7. 4 particle of mass m is confined in a one-dimensional box of length
4. Calculate the probability of finding the particle in the following region :
@) Osx « ?
[Since 2 sin’y = 1 — cos 2y]
[+2~ sna]
[Since sin nz = 0]
ele
Whenn + © P, = Quantum Mechanics-1 yy
1a ae
Gis Wits
Whennso Pret
Example 2.8. Consider an elect ”
Me 0 .
fare eteround gant electron in a box of the size of the nucleus (10 "'m)
From (2.41), we have the ground state energy
R
A
na?
ire m= 9.1% 1079 kg a=10 4m
= (6.627 x 107s)? 43.92 x 107%
8X 9.1% 10 ky x (107 4m)? 72.8 x 107%?
= 6.03 x 10717 or 3.63 10° eV.
Example 2.9. x-electrons in cyclic
polyenes may be treated as free particles
moving in a one-dimensional box of length
equal to the sum of all the carbon-carbon
bond lengths plus an additional C —C single i
bond. (see sec. 6.13). Consider 4x electrons of Ege 1659x1071 J
butadiene are moving in a box of assumed 3
length. Calculate the energies of the first $
three states and hene draw the energy level =
diagrams. 5 1
Length of the box = two carbon-carbon
double bond + two carbon-carbon single bond
= 2x 0.134nm +2 x 0.154nm
= 0.576nm
Therefore, the energy of the first three Eye 19277 x 10-8
states are given by
E,=
J
Ep = 7.271 x 10719
re
8m (0.576 nm)?
2
=——“4\__ =722 x 0"
8m (0.576 nm)
on?
E3= 2 2
8m (0.576 nm)
Example 2.10. Show that the length of the box is an integral multiple of 4/2 where
A is the wavelength associated with the particle-wave.
= 1817 x 107%
zy
Ey
= 16.359 x 1071),
2
‘h
From (2.40) we find a? = imE
‘ Liqyte P= mv}
But classically, Eagmvns, i ll a
48 Quantum Chemistry
a_inhPa? _ n?
ae
a
where n is an integer.
Graphical Interpretation
‘The graphs of the wavefunctions and the probability densities are shown in Fig. 2.6. From the
examination of these graphs it is found that
1, The wavefunctions are alternately symmetrical and antisymmetrical with respect to the
reflection from a mirror placed at the centre of the box.
2. Besides the points at the boundaries of the box, there are points inside the box where
wavefunction is zero. These points are called nodes. With the increase in the value of ‘quantum
number, the number of nodes on the wavefunction increases.
3. The probability density, | y |? has the same number of maxima as the quantum number n,
Forn = 2, the probability of finding the particle in the centre of the box is zero, which is quite
different from the classical result.
4. As we go to higher energy levels with more nodes, the maxima and the minima of probability
curves come closer together and the variations in probability along the box ultimately
becomes undetectable. For high quantum numbers, we approach the classical results of
uniform probability density. This is in agreement with the Bohr correspondence principle.
According to this principle, the quantum mechanical results must be equal to that of classical
mechanics when the quantum number describing the system becdmes very large. Though,
classical mechanics is valid for macroscopic bodies, we expect quantum mechanics to give the
same results as classical mechanics for macroscopic bodies.
E
n 3 nf
HAD Dem? of 2
34 Wolx) ° Wal) ‘ama?
ne
NAN Siem? 2 #2
“2d veto ° Wa 21 mat
et
+ 2
2 ft
14 yi60 ° wea? 14 5te
oL_ a ¢ x8
(a) (8)
Fig. 2.6 (A) Wavefunction and (8) probability density function y + » forthe
lowest three energy levels for a particle in a box. Quantum’ Mechanics-1 9
Even and Odd Functions
From the study of Fig. 26 (A) we find th . .
, ale ¥ e wavefunctions are alternately symmetric and
Sapa ene the reflection about a mirror placed at the mid-point of the box (a/2)
ay Properties, we ch: is A cle i
problem sich that a new coortionertes Se Shanes the coordinate system in the particle in a box
—a/2 whenx = 0
ne whenx = @
whenx = a/2
ic system, the range of the variable x’ is — a/2 a/2
Solve the Schrodinger equation for the particle inside the box and hence find the energy
expression of the particle,
“The Schrodinger equation forthe particle inside the box is
2
&
4 ysEy
an ae
‘As before, the solution of the equation i given as
ple) =A sin ke + B cos ke (252)
v2
8m
where kel
W
‘The boundary conditions for the system are
v(-4/2)=0 and y(a/2) =0
Introducing these conditions into (2.52) we get
Assink (a/2) + B cosk (a/2) = 0
Asin k (—a/2) +B cosk(-a/2)=0 (2538)
Since sin kx and cos kx are odd and even functions respectively, we get ater adding thes?
equations 2B cosk a/2 = 0. Quantum Mechanics-I sr
Either B=0 or coska/2=0
ka na
1B #0, then cos = 0 = cos, withn = 1,3,5, etc. or Boo, kom
Similarly, subtracting (2.53 a) from (2.53 b) we get 2.4 sink? 0
_ ka :
ILA #0, then sin'>* = 0 = sink with = 2,4,6etc.
ka _nx
or =>
2 or k= = jn = 2,4,6.. even values
IEA = Othen wavefunction (2.52) becomes yq(t) = B coskx = B cos ;n = 1,3,5.
and if B = 0, then the wavefunction becomes y,(x) =A sink =A sin ;
=2,4,6..
‘Thus, we obtain two solutions :
nme
@ ¥,@) =B cos~ 3n = 1,3,5... odd values (2.54.4)
(i) ¥,@) =A sin jn = 2,4,6 ... even values (2.54)
Now, if we substitute either of the two solutions into the Schrodinger equation, we get
wd (4 sin) = £, (4 sin)
Bam de @
where 4 (4 sin) = -
id rn? | mm
~ gam (ae
Thus, we find that the energy expression is the same as one obtained with different coordinate
representation.
‘The complete solution of the Schrodinger equation is obtained by taking the linear combination
of the two solutions (2.54).
2.9 A PARTICLE IN A THREE-
DIMENSIONAL BOX
For a particle in three-dimensional box with edges of
length a, b andc, the wave function will be a function of all three
space co-ordinates (Fig. 2.8).
‘The potential energy of the particle of mass m moving
inside the box will be zero. The remainder of space outside the ¢
box will have infinite potential energy. The potential energy at
the boundaries of the rigid walls will also be zero in order to x
avoid discontinuity of the wave function, £e., .
Veay.2) for0sx
