Solid State Physics

Homework Set 1
Solutions

January 30, 2002

1
 Ibach and Lüth Problem 1.1

The Madelung constant is a specific example of a summation in Solid-State Physics generally

known as a lattice sum. For the linear chain of ions it is more instructive to do the analytical solution
first and then the numerical solution.
The Madelung constant is defined as
X ±1
A=
pij
i6=j

Now, consider the linear chain shown below[1]:

+ − + − + − + −
The ± in the definition of the Madelung constant represents the ± ions. Starting with ion i, as
indicated in the diagram, we add up all of the ions to the right. Using rij = rpij , where r is the
nearest neighbor distance:
X ±1 X ±r
A= =
pij rij
i6=j i6=j

X ±1 µ ¶
1 1 1 1
A=r =r + − + − + ···
rij r 2r 3r 4r
i6=j

Since there are just as many ions to the left of the reference ion as there are to the right we must
multiply by a factor of 2. Thus,
µ ¶
1 1 1 1
A = 2r + − + − + ···
r 2r 3r 4r
µ ¶
1 1 1
= 2 1 − + − + ···
2 3 4

Now, using
x2 x3 x4
ln(1 + x) = x − + − + ···
2 3 4
with x = 1 we get for the Madelung constant

A = 2 ln(2) = 1.38629

Now for the numerical solution of the Madelung constant for a linear chain of ions. Below is a
FORTRAN program for calculating the Madelung constant.

2
*------------------------------------------------------------------------------*
PROGRAM MADLNG
*
* This program calculates the Madelung constant for a linear chain of
* molecules. You are asked to give the number of iterations required
* for the sum. To stop the program type -1 when asked for the number
* of iterations. The results of the program are printed out in a file
* called RESULT.
*
INTEGER L,NUM
REAL A, SUM
*
OPEN(UNIT = 10, FILE = ’RESULT’, STATUS = ’NEW’)
*
WRITE(10,*) ’Iteration’, ’ Constant’
5 PRINT*,’Enter the number of iterations for the sum:’
READ*, NUM
*
IF(NUM.EQ.-1) GOTO 20
SUM = 0.0
*
DO 10 L = 1, NUM
SUM = SUM + REAL((-1)**(L+1))/REAL(L)
10 CONTINUE
*
A=2*SUM
*
WRITE(10,*) NUM, A
GOTO 5
20 STOP
END
*------------------------------------------------------------------------------*

The result of running this program is (this is the file called RESULT):

Iteration Constant
1000 1.38529
2000 1.38579
3000 1.38595
4000 1.38604
5000 1.38609
6000 1.38612
7000 1.38614
8000 1.38616
9000 1.38617
10000 1.38618

Note that 4000 iterations are required to get convergence to just three decimal places!!! After
10,000 iterations we did not get convergence to 5 decimal places. This is a general problem with doing
lattice sums. It is very dificult to get convergence. This is especially true of a three dimensional lattice
where convergence is not always possible.
This sum can also be done using Mathematica. The following is an example of the Mathematica
output
In[1]:=
a = Sum[((-1)^(n+1))/n,{n,1,Infinity}]

Out[1]:=
1 + n
(-1)
Sum[---------, {n, 1, Infinity}]
n

3
 Mathematica is trying to be exact. If we want a numerical answer we will have to tell Mathematica
to do it.

In[2]:=
mc = 2*N[a]

Out[2]:=
1.38629

Note that Mathematica gives you an answer that is correct to however many decimal places you
request.
Next, we will calculate numerically the Madelung constant for the NaCl lattice in three dimensions
using the screened Coulomb potential:

±e2 −αrij
φij = e
4π²0 rij

This sum will converge because ofpthe exponential.

Using rij = rpij where pij = i2 + j 2 + k 2 and choosing α to have units of r we can rewrite the
above equation in the form:
±e2
φij = e−αpij
4π²0 rpij
The Madelung constant will then be defined as
X ±e−αpij
A=
pij
i6=j6=k

Since we do not know α we should compute the sum as a function of various values of α and
then plot the results. This will yield a graph of Madelung constant versus α. Below is a FORTRAN
program for calculating the Madelung constant in three dimensions for the NaCl lattice.

4
 *------------------------------------------------------------------------------*
PROGRAM MC3D
*
* This program computes the Madelung constant for NaCl using a
* screened Coulomb interaction. The results are printed out in a
* file called NACL. You will be prompted for the number of iterations
* for the sum.
*
IMPLICIT NONE
INTEGER I,J,K,nsum
REAL SUM, P, ALPHA
*
OPEN(UNIT = 10, FILE = ’NACL’, STATUS = ’UNKNOWN’)
*
WRITE(10,*) ’# ALPHA Constant’
ALPHA = 1.0
WRITE(6,*) ’Enter the number of iterations’
READ(5,*) nsum

5 SUM = 0.0
*
DO 30 I = -nsum,nsum
DO 20 J = -nsum,nsum
DO 10 K = -nsum,nsum
P = SQRT(REAL(I)**2 + REAL(J)**2 + REAL(K)**2)
IF(P.NE.0.0) THEN
SUM = SUM - ((-1.)**(I+J+K))*EXP(-ALPHA*P)/P
ENDIF
10 CONTINUE
20 CONTINUE
30 CONTINUE
*
WRITE(10,*) ALPHA, SUM
*
ALPHA = ALPHA - 0.1
IF(ALPHA.GT.0.0) GOTO 5
*
STOP
END
*------------------------------------------------------------------------------*

5
 The output of this program is given below.

ALPHA Constant
1.00000 0.934673
0.900000 0.999754
0.800000 1.06821
0.700000 1.14024
0.600000 1.21588
0.500000 1.29503
0.400000 1.37800
0.300000 1.46472
0.200000 1.55522
9.99999E-02 1.64871

This data was plotted as shown below.

1.8
Madelung Constant

1.6
fit
1.4

1.2

1.0

0.8
0.0 0.2 0.4 0.6 0.8 1.0
α

This data was fit with the following quadratic equation

ax2 + bx + c

where the constants have the following values:

a = 0.118302
b = −0.995
c = 1.7469

The y-intercept, c = 1.7469, which is the extrapolated value as well is the Madelung constant for
the NaCl structure.

6
 Ibach and Lüth Problem 1.2

The binding energy per site is determined by

e2 X ±1 B X 1
Φ/N = − + n
r pij r pnij
i6=j i6=j

where r is the near-neighbor distance and n and B are determined empirically. It is unclear what Ibach
and Lüth means by the binding energy, but it is clear that the the first term in the equation above will
decrease as the cation radius (and r) decreases increasing the binding energy. Of course, the second
term, meant to model the potential repulsion between the two electron clouds of the constituent ions,
will increase as the cation radius (and r) decreases. In fact, it is the balancing of these two terms
which determines the ionic radius.
The equilibrium near-neighbor distance r0 is given by the condition
d
(Φ/N ) = 0
dr
or
nBC X ±1 X 1
r0n−1 = A= C=
e2 A pij pnij
i6=j i6=j

Now we must determine how C and A change with lattice structure to see the effect of changing the
near-neighbor distance r0 . This may be done using a method very similar to that employed in the
first problem to calculate the Madelung constant A. For example, for CsCl we may calculate A and
C with the code:

c This program calculates the Madelung constant and

c
c C = sum 1/p^n
c
c for a CsCl, or ionic bcc, structure structure, the primitive
c lattice vectors are
c
c a_1= ( x + y - z )/2
c a_2= (-x + y + z )/2
c a_3= ( x - y + z )/2
c
c The length of the vector i a_1 + j a_2 + k a_3 is
c then (in terms of the nearest-neighbor distance):
c
c sqrt( (i-j+k)**2 + (i+j-k)**2 + (-i+j+k)**2)/sqrt(3.0)

open(unit=8,file=’A_CsCl.dat’,status=’unknown’)
write(6,*) ’enter range,n’
read(5,*) range,n_free

do 10 alpha=0.1,1.0,0.1

n=int(range/alpha)
A=0.0
C=0.0
do i=-n,n
do j=-n,n
do k=-n,n
r_n=sqrt(float( (i-j+k)**2 +
. (i+j-k)**2 + (-i+j+k)**2))/sqrt(3.0)
if(r_n.ne.0.0) then

7
 A=A-((-1)**(i+j+k))*exp(-alpha*r_n)/r_n
C=C+1.0/r_n**n_free
end if
end do
end do
end do
write(6,*) ’ alpha= ’,alpha,’ A= ’,A,’ C= ’,C
write(8,*) alpha,A,C

10 end do
stop
end

A and C may be calculated by extrapolating the data. For n = 5:

# alpha A C
0.100000 1.66492 14.7470
0.200000 1.57015 14.7454
0.300000 1.47976 14.7423
0.400000 1.39302 14.7380
0.500000 1.30983 14.7290
0.600000 1.23051 14.7154
0.700000 1.15475 14.6992
0.800000 1.08254 14.6716
0.900000 1.01382 14.6500

A similar code was developed for NaCl. For CsCl I get A = 1.7625 and C = 14.748, and for NaCl I
get A = 1.7477 and C = 10.369. The ratio C/A = 5.93 for NaCl, and C/A = 8.368 for CsCl. Clearly,
as r0 decreases, the NaCl structure has a better equilibrium position. This demonstrates that, as far
as the crystal structure is concerned, avoiding overlap of the electronic cores is more important than
the Madelung energy since C changes more with crystal structure than does A. This also ignores the
dependence of B on the crystal structure. B should depend upon the near-neighbor distance, since we
want the corresponding potential to become strongly positive when the ionic cores begin to overlap.
Therefore, one expects that roughly B ∝ (ranion + rcation )n (rCl = 1.81, rN a = 0.97 and rCs = 1.67).
Thus, B will be much larger for the CsCl structure than for the NaCl structure, further favoring the
NaCl structure when when the cation radius increases. A more precise and meaningful total energy
calculation would require a more precise knowledge of B and n.
As discussed in Kittel[1] Table 7, many other ionic crystals form with a NaCl structure. In each
case, the mismatch between the ionic radii, ranion /rcation > 1.4 (cf. table 9 in Kittel[1]). For example,
in LiF rF /rLi = 1.36/0.68 = 2, in RbI rI /rRb = 2.16/1.48 = 1.46.

8
 Ibach and Lüth Problem 1.4

Condsider a dipole, p, a distance d away from a neutral wall that is infinite in extent. The dipole,
p, will induce a dipole moment, p0 , in the wall given by
αp
p0 = αE =
d3
Where α is the polarizibility of the wall. Now, we need to determine the electric field E 0 a the position
of the dipole, p, due to the induced dipole, p0 , of the wall.

p0
P=
V
Where P is the polarization and V is the volume of the wall. The induced charge on the surface of
the wall is
α α
σb = n · P = n·p= p
V d3 V d3
Now, we must determine the electric field at d due to the induced charge σb in the wall.
Z
1 σb (dez − ρeρ )d2 r
E0 =
4π²0 (d2 + ρ2 )3/2

Z 2π Z ∞
σb d ρdρdφ
Ez0 =
4π²0 0 (d + ρ2 )3/2
2
Z ∞0
σb d ρdρ
= 2π
4π²0 0 (d + ρ2 )3/2
2
à !¯∞
σb d −1 ¯
¯
= p ¯
2²0 ρ + d ¯0
2 2
µ ¶
σb d 1
= 0+
2²0 d
σb
=
2²0
Thus,
σb α p2
U = p · E0 = p=
2²0 2²0 V d3

9
 Ibach and Lüth Problem 1.6

The bulk modulus is given by

∂P
κ = −V
∂V
Using P = −∂U/∂V and u = U/N , v = V /N we can rewrite the bulk modulus in the following way 1
µ ¶
∂ ∂u
κ=v
∂v ∂v

The lattice constant for the NaCl structure is represented by a. The nearest neighbor distance is
r = a/2. The volume/particle of the NaCl structure is

a3
v=
4
The 4 is there because there are 4 NaCl molecules per cube. The specific volume can be written in
terms of the nearest neighbor distance, r, in the following way
3
(2r) 8r3
v= = = 2r 3
4 4
We now wish to rewrite the bulk modulus in terms of partial derivatives involving the nearest neighbor
distance, r. Using the following differential

dv = 6r 2 dr

we have
∂ 1 ∂
= 2
∂v 6r ∂r
Thus the bulk modulus can be written as
µ ¶µ ¶
1 ∂ 1 ∂u
κ = 2r 3
6r2 ∂r 6r2 ∂r
µ ¶
r ∂ 1 ∂u
=
3 ∂r 6r2 ∂r
µ ¶
r ∂ 1 ∂u
=
18 ∂r r2 ∂r

We need to evaluate the Bulk modulus at the equilibrium separation r0

à ¯ ¯ !
r −1 ∂u ¯¯ 1 ∂ 2 u ¯¯
κ= +
18 r3 ∂r ¯r=r0 r2 ∂r2 ¯r=r0

where I have expanded the derivative. At equilibrium

¯
∂u ¯¯
=0
∂r ¯r=r0

Thus ¯
1 ∂ 2 u ¯¯
κ=
18r0 ∂r2 ¯r=r0
For the internal energy we were asked to use equation 1.11 in Ibach and Lüth.

−Ae2 B
u= +
4π²0 r rn
1 Whenever a quantity, such as the internal energy U or the volume V , is divided by the total number of particles,

N , in a system that quantity is referred to as the specific quantity. For example, v = V /N is referred to as the specific
volume.

10
In the above equation A is the Madelung constant and B must be determined in terms of the equilib-
rium separation distance, r0 . Thus
∂u Ae2 nB
= 2
− n+1
∂r 4π²0 r r
¯
¯
∂u ¯ Ae2 nB
¯ =0 ⇒ = n+1
∂r r=r0 4π²0 r02 r0
Thus
Ae2 r0n+1
B=
4π²0 nr02
Substituting this back into u yields

−Ae2 Ae2 r0n+1 1

u = +
4π²0 r 4π²0 nr02 rn
µ ¶
Ae2 −1 r0n+1 1
= +
4π²0 r nr02 rn
Now we must compute the bulk modulus in terms of r0 :
µ ¶
∂u Ae2 1 r0n+1 1
= − n
∂r 4π²0 r2 nr02 rn+1
µ ¶
∂2u Ae2 −2 r0n+1 (n + 1)
= + 2
∂r2 4π²0 r3 r0 rn+2
¯ µ ¶
∂ 2 u ¯¯ Ae2 −2 r0n+1 (n + 1)
= + 2
∂r2 ¯r=r0 4π²0 r03 r0 r0n+2
µ ¶
Ae2 −2 (n + 1)
= +
4π²0 r03 r03
Ae2 (n − 1)
=
4π²0 r03
Thus, the bulk modulus is µ ¶
Ae2 n−1
κ=
4π²0 18r04
Next, we are asked to determine the lattice constant, the Madelung constant, and the binding energy
of the NaCl structure. We have the following three equations
µ ¶
Ae2 n − 1
κ=
4π²0 18r04
B 4π²0 n
r0n−1 =
A e2
µ ¶
−Ae2 n − 1
u (r0 ) =
4π²0 r0 n
with 5 unknowns: A, B, n, r0 , and u. Thus, we’re going to have to make some assumptions. The
bulk modulus is a measured quantity equal to
N dynes
κ = 2.4 × 1010 = 2.4 × 1011
m2 cm2
The lattice constant is also a measured quantity. It is determined from x-ray diffraction on a powdered
sample. Its value is given as
a = 5.64 Å
Thus, the nearest neighbor distance is
a
r0 = = 2.82 Å = 2.82 × 10−10 m
2

11
The Madelung constant is determined by some other method, such as in Ibach and Lüth Problem
1.1 and has the value
A = 1.7476
Now we can determine n and u (r0 ). Solving the previous equation for n yields

4π²0 18r04
n=1+ κ
e2 A
Substituting the numerical values yields
n = 7.77
this is the way n is determined in real life Physics. Now making the appropriate numerical substitutions
into the equation for u (r0 ) gives
u (r0 ) = −7.8 eV

12
 Ibach and Lüth Problem 1.9

(a) The contour plots are done using Mathematica

In[1]:=
s = Exp[-Sqrt[x^2 + y^2]]*(1 - Sqrt[x^2 + y^2])

Out[1]:=

2 2
1 - Sqrt[x + y ]
-----------------
2 2
Sqrt[x + y ]
E

In[2]:=
ContourPlot[s,{x,-5,5},{y,-5,5},
ContourShading -> False]

-2

-4

-4 -2 0 2 4

Out[2]:=
-ContourGraphics-

13
In[3]:=
px = Exp[-Sqrt[x^2 + y^2]]*x

Out[3]:=

x
--------------
2 2
Sqrt[x + y ]
E

In[4]:=
ContourPlot[s,{x,-5,5},{y,-5,5},
ContourShading -> False]

-2

-4

-4 -2 0 2 4

Out[4]:=
-ContourGraphics-

¡ ¢
(b) We are asked to show that the orthonormality requirement for the ψi 2sp3 wave functions
leads to the following condition X
aij akj = δik
j

14
First let X X
ψi = ail φl and ψj = ajm φm
l m

with
hψi | ψj i = δij
X X
hψi | ψj i = a∗il φ∗l ajm φm
l m
XX
= a∗il ajm φ∗l φm
l m
XX
= a∗il ajm δlm
l m
X
= a∗il ajl
l
X
= ail ajl = δij
l

(c) In order to choose the four possible functions ψi which satisfy the orthonormality requirement
we first choose ψ1 to have positive coefficients
1 1 1 1
ψ1 = φ1 + φ2 + φ3 + φ4
2 2 2 2
Next choose
ψ2 = aφ1 + bφ2 + cφ3 + dφ4
ψ2 must be normalized which requires

a2 + b 2 + c 2 + d 2 = 1

and we must require that ψ2 be orthogonal to ψ1 , thus

1 1 1 1
a+ b+ c+ d=0
2 2 2 2
a+b+c+d=0
Since a, b, c, d = ± 21 a possible choice is
1 1
a=b= and c = d = −
2 2
Thus
1
ψ2 = (φ1 + φ2 − φ3 − φ4 )
2
Next, choose
ψ3 = aφ1 + bφ2 + cφ3 + dφ4
ψ3 must be normalized and orthogonal to both ψ1 and ψ2 . Thus

a2 + b 2 + c 2 + d 2 = 1
1 1 1 1
a+ b+ c+ d=0
2 2 2 2
1 1 1 1
a+ b− c− d=0
2 2 2 2
1
Again, a, b, c, d = ± 2 , thus, the orthogonality conditions yield
1 1
b = −a = and d = −c =
2 2
Thus
1
ψ3 = (φ1 − φ2 + φ3 − φ4 )
2

15
Following the same procedure we choose

ψ4 = aφ1 + bφ2 + cφ3 + dφ4

ψ4 must be normalized and orthogonal to ψ1 , ψ2 , and ψ3 . These conditions yield

a2 + b 2 + c 2 + d 2 = 1
1
(a + b + c + d) = 0
2
1
(a + b − c − d) = 0
2
1
(a − b + c − d) = 0
2
The above conditions require
a = −b = −c = d
Thus
1
ψ4 = (φ1 − φ2 − φ3 + φ4 )
2
In summary, the four 2sp3 states are
1
ψ1 = (φ1 + φ2 + φ3 + φ4 )
2
1
ψ2 = (φ1 + φ2 − φ3 − φ4 )
2
1
ψ3 = (φ1 − φ2 + φ3 − φ4 )
2
1
ψ4 = (φ1 − φ2 − φ3 + φ4 )
2
(d) The tetrahedral direction of the orbitals in part(c) could be shown using a 3-D plot in Math-
ematica; however, in order to do this analytically we must first discuss p-orbitals in an arbitrary
direction u, usually referred to as a pu orbital.
Normally, we think of the p-orbitals extending along the x, y, and z axes. But the choice of the
Ox, Oy, and Oz directions (O is for the origin) is arbitrary, thus, by a linear superposition of the p x ,
py , and pz orbitals we should be able to construct an orbital, pu , along an arbitrary axis, Ou.
Let Ou be an axis forming angles α, β, and γ with Ox, Oy, and Oz respectively. Then the direction
cosines obey the following condition[2]

cos2 α + cos2 β + cos2 γ = 1

This is really a normality condition for a quantum mechanical state. Thus, we can create the following
state
r h
3 x y zi
cos α |px i + cos β |py i + cos γ |pz i = Rn,1 (r) cos α + cosβ + cos γ
4π r r r
r
3 u
= Rn,1 (r)
4π r
Where Rn,1 (r) is the radial part of the hydrogenic wave function and

u = x cos α + y cos β + z cos γ

Thus, the above state can be thought of as a pu orbital in the Ou direction. Therefore, any real,
normalized linear superposition of px , py , and pz orbitals, such as

cos α |px i + cos β |py i + cos γ |pz i

is a pu orbital. Thus, the coefficients in front of the basis orbitals px , py , and pz are the direction
cosines of the pu orbital.

16
 Now, consider the four states, ψi , from part(c). Since the s-state has no θ or φ dependence it does
not contribute to the direction of the orbitals. So, just consider the p-orbitals.

1
ψ1 ∝ √ (px + py + Pz ) [1, 1, 1]
3
1
ψ2 ∝ √ (px − py − Pz ) [1, −1, −1]
3
1
ψ3 ∝ √ (−px + py − Pz ) [−1, 1, −1]
3
1
ψ4 ∝ √ (−px − py + Pz ) [−1, −1, 1]
3
Note, that the orbitals have been renormalized; however, the directions have been retained as
indicated by the Miller indices in square brackets. Thus, ψ1 is in the direction u1 = √13 (ex + ey + ez )
and the other ψi ’s have directions as follows
1
ψ2 ⇒ u2 = √ (ex − ey − ez )
3
1
ψ3 ⇒ u3 = √ (−ex + ey − ez )
3
1
ψ4 ⇒ u4 = √ (−ex − ey + ez )
3

Thus, the direction between ψ1 and ψ2 is

1 1 1 1
u1 · u2 = |u1 | |u2 | cos θ = − − =−
3 3 3 3
which yields
1
cos θ = − ⇒ θ = 109.47◦
3
Likewise, the angle between ψ1 and ψ3 is
1 1 1 1
u1 · u3 = cos θ = − + − = −
3 3 3 3
which yields θ = 109.47◦ . Thus, the angle between any two orbitals is 109.47◦ .
(e) This part can be done using Mathematica to perform the symbolic manipulation. Of course,
you can always do it by hand.

In[1]:= s = c Exp[-rho] (1 - rho)

c (1 - rho)
Out[1]= -----------
rho
E

In[2]:= px = c Exp[-rho] rho Sin[theta] Cos[phi]

c rho Cos[phi] Sin[theta]

Out[2]= -------------------------
rho
E

In[3]:= py = c Exp[-rho] rho Sin[theta] Sin[phi]

c rho Sin[phi] Sin[theta]

Out[3]= -------------------------

17
 rho
E

In[4]:= pz = c Exp[-rho] rho Cos[theta]

c rho Cos[theta]
Out[4]= ----------------
rho
E

In[5]:= psi1 = 1/2 (s + px + py + pz)

c (1 - rho) c rho Cos[theta] c rho Cos[phi] Sin[theta]

Out[5]= (----------- + ---------------- + ------------------------- +
rho rho rho
E E E

c rho Sin[phi] Sin[theta]

> -------------------------) / 2
rho
E

In[6]:= psi2 = 1/2 (s + px - py - pz)

c (1 - rho) c rho Cos[theta] c rho Cos[phi] Sin[theta]

Out[6]= (----------- - ---------------- + ------------------------- -
rho rho rho
E E E

c rho Sin[phi] Sin[theta]

> -------------------------) / 2
rho
E

In[7]:= psi3 = 1/2 (s - px + py - pz)

c (1 - rho) c rho Cos[theta] c rho Cos[phi] Sin[theta]

Out[7]= (----------- - ---------------- - ------------------------- +
rho rho rho
E E E

c rho Sin[phi] Sin[theta]

> -------------------------) / 2
rho
E

In[8]:= psi4 = 1/2 (s - px - py + pz)

c (1 - rho) c rho Cos[theta] c rho Cos[phi] Sin[theta]

Out[8]= (----------- + ---------------- - ------------------------- -
rho rho rho
E E E

c rho Sin[phi] Sin[theta]

> -------------------------) / 2
rho
E

18
In[9]:= a = psi1^2 + psi2^2 + psi3^2 + psi4^2

c (1 - rho) c rho Cos[theta] c rho Cos[phi] Sin[theta]

Out[9]= Power[----------- + ---------------- - ------------------------- -
rho rho rho
E E E

c rho Sin[phi] Sin[theta]

> -------------------------, 2] / 4 +
rho
E

c (1 - rho) c rho Cos[theta] c rho Cos[phi] Sin[theta]

> Power[----------- - ---------------- + ------------------------- -
rho rho rho
E E E

c rho Sin[phi] Sin[theta]

> -------------------------, 2] / 4 +
rho
E

c (1 - rho) c rho Cos[theta] c rho Cos[phi] Sin[theta]

> Power[----------- - ---------------- - ------------------------- +
rho rho rho
E E E

c rho Sin[phi] Sin[theta]

> -------------------------, 2] / 4 +
rho
E

c (1 - rho) c rho Cos[theta] c rho Cos[phi] Sin[theta]

> Power[----------- + ---------------- + ------------------------- +
rho rho rho
E E E

c rho Sin[phi] Sin[theta]

> -------------------------, 2] / 4
rho
E

In[10]:= b = Simplify[a]

2 2
c (1 - 2 rho + 2 rho )
Out[10]= -----------------------
2 rho
E

(f) Carbon has four orbitals in its valence shell. These are the 2s, 2px , 2py , and 2pz orbitals. The
2s orbital has a bond strenght of 1 and the three 2p orbitals have a bond strength of 1.732. When
an atom forms a molecular bond it does so in a way that will minize its energy. The larger the bond
strength the smaller the energy. Thus, if the 2s and 2p orbitals can combine in some way to increase
the bond strength, thus decreasing the energy, they will do so. By forming a 2sp 3 hybridized orbital
the bond strength will increase to 2. Thus, the energy will be lower and the molecule will form bonds
in a teteahedral direction[3].

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References
[1] Kittel, Charles. Introduction to Solid State Physics. New York: John Wiley & Sons, 1986.

[2] Cohen-Tannoudji, Claude, Bernard Diu, and Frank Laloe. Quantum Mechanics. New York: John
Wiley & Sons.

[3] Pauling, Linus. The Nature of the Chemical Bond: And the Structure of Molecules and Crystals:
An Introduction to Modern Structural Chemistry. Ithaca, New York: Cornell University Press,
1940.

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