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Finally using the normalisation of |0i, show numerically that c2 0.3795. What value do you get
for the probability of the oscillator remaining in the ground state?
Show that at the end of the experiment the expectation value of the energy is 0.2656h. Explain
physically why this is less than the original ground-state energy 12 h.
This example contains the physics behind the inflationary origin of the universe: gravity explo-
sively enlarges the vacuum, which is an infinite collection of harmonic oscillators (Problem 3.13).
Excitations of these oscillators correspond to elementary particles. Before inflation the vacuum is
unexcited so every oscillator is in its ground state. At the end of inflation, there is non-negligible
probability of many oscillators being excited and each excitation implies the existence of a newly
created particle.
Soln: From Problem 3.6 we have
mx + ip mf 2 x + ip
A A p
2m h 2mhf 2
x i fx i
= + p = + p
2 h
2 f h
Hence
f 2i 1 f
A + A = x A A = f p so A = (A + A ) + (A A )
f h 2f 2
X
0 = A|0i = 21 (f 1 + f )ck A |k i + (f 1 f )ck A |k i
k
Xn
1
o
= 1
2 (f + f ) kck |k 1 i + (f 1 f ) k + 1ck |k + 1 i
k
Multiply through by hn |:
0 = (f 1 + f ) n + 1cn+1 + (f 1 f ) ncn1 ,
which is a recurrence relation from which all non-zero cn can be determined in terms of c0 . Put
c0 = 1 and solve for the cn . Then evaluate S |cn |2 and renormalise: cn Pcn / S.
The probability of remaining in the ground state is |c0 |2 = 0.8. hEi = n |cn |2 (n + 21 )
hf 2 . It
is less than the original energy because of the chance that energy is in the spring when the stiffness
is reduced.
3.16 In terms of the usual ladder operators A, A , a Hamiltonian can be written
H = A A + (A + A ). (3.5)
What restrictions on the values of the numbers and follow from the requirement for H to be
Hermitian?
Show that for a suitably chosen operator B, H can be rewritten
H = B B + constant, (3.6)
where [B, B ] = 1. Hence determine the spectrum of H.
Soln: Hermiticity requires and to be real. Defining B = A + a with a a number, we have
[B, B ] = 1 and
H = (B a )(B a) + (B a + B a ) = B B + ( a )B + ( a)B + (|a|2 (a + a )).
We dispose of the terms linear in B by setting a = /, a real number. Then H = B B 2 /.
From the theory of the harmonic oscillator we know that the spectrum of B B is 0, 1, . . ., so the
spectrum of H is n 2 /.
3.17 Numerically calculate the spectrum of the anharmonic oscillator shown in Figure 3.2. From
it estimate the period at a sequence of energies. Compare your quantum results with the equivalent
classical results.
Soln:
3
3.18 Let B = cA + sA , where c cosh , s sinh with a real constant and A, A are the
usual ladder operators. Show that [B, B ] = 1.
Consider the Hamiltonian
H = A A + 21 (A A + AA), (3.7)
where and are real and such that > > 0. Show that when
c s = Ec, c s = Es (3.8)
with E a constant, [B, H] = EB. Hence determine the spectrum of H in terms of and .
Soln:
[B, B ] = [cA + sA , cA + sA] = (c2 s2 )[A, A ] = 1
[B, H] = [cA + sA , A A + 12 (A A + AA)] = c[A, A A + 12 A A ] + s[A , A A + 21 AA]
= c(A + A ) s(A + A) = cEA + sEA = EB
as required. Let H|E0 i = E0 |E0 i. Then multiplying through by B
E0 B|E0 i = BH|E0 i = (HB + [B, H])|E0 i = (HB + EB)|E0 i
So H(B|E0 i) = (E0 E)(B|E0 i), which says the B|E0 i is an eigenket for eigenvalue E0 E.
We assume that the sequence of eigenvalues E0 , E0 E, E0 2E, . . . terminates because B|Emin i =
0. Mod-squaring this equation we have
0 = hEmin |B B|Emin i = hEmin |(cA + sA)(cA + sA )|Emin i
= hEmin |{(c2 + s2 )A A + s2 + cs(A A + AA)}|Emin i
= cshEmin |{(c/s + s/c)A A + s/c + (A A + AA)}|Emin i
But eliminating E from the given equations, we find (c/s + s/c) = 2. Putting this into the last
equation
2
0 = hEmin | A A + s/c + (A A + AA) |Emin i
Multiplying through by /2 this becomes
0 = hEmin |{H + s/2c}|Emini
so Emin = s/2c. Finally, x = s/c satisfies the quadratic
r
2 2
x 2 x+1=0 x= 1.
2
Also from the above E = x so the general eigenenergy is
p
En = Emin + nE = 21 x + n nx = n (n + 21 )x = n (n + 12 ) 2 2
p
= 21 (n + 21 ) 2 2
We have to choose the plus sign in order to achieve consistency with our previously established value
of Emin ; thus finally p
En = 12 + (n + 21 ) 2 2
4.2 Show that the vector product a b of two classical vectors transforms like a vector under
T
rotations. Hint: A rotation
P matrix R satisfies
P the relations R R = I and det(R) = 1, which in
tensor notation read p Rip Rtp = it and ijk ijk Rir Rjs Rkt = rst .
4
4.3 We have shown that [vi , Jj ] = i k ijk vk for any operator whose components vi form a
P
vector. The expectation value of this operator relation in any state |i is then h|[vi , Jj ]|i =
i k ijk h|vk |i. Check that with U () = eiJ this relation is consistent under a further rotation
P
|i | i = U ()|i by evaluating both sides separately.
Soln: Under the further rotation the LHS h|U [vi , Jj ]U |i. Now
U [vi , Jj ]U = U vi Jj U U Jj vi U = (U vi U )(U Jj U ) (U Jj U )(U vi U )
X X
= [Rik vk , Rjl Jl ] = Rik Rjl [vk , Jl ].
kl kl
Similar |i U |i on the RHS yields
X
i Rkm ijk h|vm |i.
km
We now multiply each side by Ris Rjt and sum over i and j. On the LHS this operation yields
[vs , Jt ]. On the right it yields
X X
i Ris Rjt Rkm ijk h|vm |i = i stm h|vm |i,
ijkm m
Figure 5.0 The real part of the wavefunction when a free particle of energy E is scattered by a classically forbidden
square barrier barrier (top) and a potential well (bottom). The upper panel is for a barrier of height V0 = E/0.7 and
half-width a such that 2mEa2 / h2 = 1. The lower panel is for a well of depth V0 = E/0.2 and half-width a such that
2
2
2mEa / h = 9. In both panels (2mE/ h2 )1/2 = 40.
that the wavefunctions of these states are related by uk (x) = eiak uk (x) and uk (x) = uk (x a).
Hence obtain equation (4.4).
Soln: U (a)|ki is the result of translating a state of well-defined momentum by k. Moving to the
position representation
uk (x) = hx|U (a)|ki = hk|U (a)|xi = hk|x ai = uk (x a)
Also
hx|U (a)|ki = hx|eiap/h |ki = eiak hx|ki = eiak uk (x)
Putting these results together we have uk (x a) = eiakuk (x). Setting a = x we find uk (x) =
eikx uk (0), as required.
5.13 This problem is about the coupling of ammonia molecules to electromagnetic waves in an
ammonia maser. Let |+i be the state in which the N atom lies above the plane of the H atoms and
|i be the state in which the N lies below the plane. Then when there is an oscillating electric field
E cos t directed perpendicular to the plane of the hydrogen atoms, the Hamiltonian in the |i basis
becomes
E + qEs cos t A
H= . (5.1)
A E qEs cos t
Transform this Hamiltonian from the |i basis
to the basis provided by the states of well-defined
parity |ei and |oi (where |ei = (|+i + |i)/ 2, etc). Writing
|i = ae (t)eiEe t/h |ei + ao (t)eiEo t/h |oi, (5.2)
7
condition ae (0) = 0. With a0 (0) = 1 we get from the original equations the second initial condition
a e (0) = i. For trial solution ae et the auxiliary eqn is
h p i
2 i( 0 ) + 2 = 0 = 12 i( 0 ) ( 0 )2 42 = i
h i
with = 12 ( 0 ) ( 0 )2 + 42 . When 0 , these frequencies both lie close to .
p
From the condition ae (0) = 0, the required solution is ae (t) (ei+ t ei t ) and the constant of
proportionality follows from the second initial condition, so finally
ae (t) = p (ei+ t ei t ) ()
( 0 )2 + 42
The probability oscillates between the odd and even states. First the oscillating field stimulates
emission of radiation and decay from |oi to |ei. Later the field excites molecules in the ground state
to move back up to the first-excited state |oi.
If we solve the original equations (1) exactly on resonance ( = 0 ), the relevant solution is
ae (t) = 12 (eit eit ),
which is what our general solution () reduces to as 0 .
5.15 Particles of mass m and momentum hk at x < a move in the potential
0 for x < a
(
V (x) = V0 12 [1 + sin(x/2a)] for |x| < a (5.5)
1 for x > a,
where V0 < h2 k 2 /2m. Numerically reproduce the reflection probabilities plotted in Figure 5.20 as
follows. Let i (xj ) be the value of the wavefunction at xj = j, where is a small increment
in the x coordinate. From the tise show that
j (2 2 k 2 )j+1 j+2 , (5.6)
p
where k 2m(E V )/ h. Determine j at the two grid points with the largest values of x from
a suitable boundary condition, and use the recurrence relation (5.6) to determine j at all other
grid points. By matching the values of at the points with the smallest values of x to a sum of
sinusoidal waves, determine the probabilities required for the figure. Be sure to check the accuracy
of your code when V0 = 0, and in the general case explicitly check that your results are consistent
with equal fluxes of particles towards and away from the origin.
Equation (12.40) gives an analytical approximation for in the case that there is negligible
reflection. Compute this approximate form of and compare it with your numerical results for
larger values of a.
Soln:
We discretise the tise
h2 d2
h2 j+1 + j1 2j
2
+ V = E by + Vj j = Ej
2m dx 2m 2
9
which readily yields the required recurrence relation. At the right-hand boundary we require a pure
outgoing wave, so j = exp(ijK) gives at the two last grid points. From the recurrence relation
we obtain elsewhere. At the left boundary we solve for A+ and A the equations
A+ exp(i0k) + A exp(i0k) = 0
A+ exp(i1k) + A exp(i1k) = 1
The transmission probability is (K/k)/|A+ |2 . The code must reproduce the result of Problem 5.4
in the appropriate limit.
5.16 In this problem we obtain an analytic estimate of the energy difference between the even-
and odd-parity states of a double square well. Show that for large , coth tanh 4e2 . Next
letting k be the difference between the k values that solve
s p
W2 coth W 2 (ka)2 even parity
tan [r k(b a)] 2
1= p (5.7a)
(ka) tanh W 2 (ka)2 odd parity,
where r
2mV0 a2
W (5.7b)
h2
for given r in the odd- and even-parity cases, deduce that
" 1/2 1/2 # 1
W2 W2 (ka)2
1
1 + 1 (b a) + 1 k
(ka)2 (ka)2 k W2 (5.8)
h p i
4 exp 2 W 2 (ka)2 .
Hence show that when W 1 the fractional difference between the energies of the ground and first
excited states is
E 8a
e2W 1E/V0 . (5.9)
E W (b a)
Soln: First
e + e e e 1 + e2 1 e2
coth tanh =
= 2
(1 + 2e2 ) (1 2e2 ) = 4e2
e e e +e 1e 1 + e2
So when W 1 the difference in the right side of the equations for k in the cases of even and odd
parity is small and we may estimate the difference in the left side by its derivative w.r.t. k times the
difference k in the solutions. sThat is
W2 W 2 /(ka)2 k/k 2 2
s2 [r k(b a)](b a)k 2
1 + tan[r k(b a)] q 2 4e2 W (ka)
(ka) W
(ka)2 1
In the case of interest the right side of the original equation is close to unity, so we can simplify the
last equation by using s
W2
tan [r k(b a)] 11
(ka)2
With the help of the identity s2 = 1 + tan2 we obtain the required relation. We now approximate
the left side for W ka. This yields
W 2
(b a)k 4e2W 1(ka/W ) ($)
ka
Since E = h2 k 2 /2m, E/E = 2k/k and
2mEa2 h2
(ka/W )2 = = E/V0 .
h2 2mV0 a2
The required relation follows when we use these relations in ($).
10
6.11 Show that when the density operator takes the form = |ih|, the expression Q = Tr Q for
the expectation value of an observable can be reduced to h|Q|i. Explain the physical significance
of this result. For the given form of the density operator, show that the equation of motion of
yields
|i
|ih| = |ih| where |i ih H|i. (6.1)
t
Show from this equation that |i = a|i, where a is real. Hence determine the time evolution of |i
given the at t = 0, |i = |Ei is an eigenket of H. Explain why does not depend on the phase of
|i and relate this fact to the presence of a in your solution for |, ti.
Soln: X
Tr(Q) = hn|Q|ih|ni
n
We choose a basis that |i is a member. Then there is only one non-vanishing term in the sum,
when |ni = |i, and the right side reduces to h|Q|i as required. This result shows that density
operators recover standard experimental predictions when the system is in a pure state.
Differentiating the given we have
d |i h| 1
= h| + |i = (H|ih| |ih|H)
dt t t ih
Gathering the terms proportional to h| on the left and those proportional to |i on the right we
obtain the required expression. Now
|ih| = |ih| |ih|i = |ih|i,
which establishes that |i |i. We define a as the constant of proportionality. Using |i = a|i
in |ih| = |ih| we learn that a = a so a is real.
Returning to the definition of |i we now have
|i
ih = (H a)|i.
t
This differs from the tdse in having the term in a. If |i is an eigenfunction of H, we find that its
time dependence is |, ti = |, 0iei(Ea)t/h rather than the expected result |, ti = |, 0ieiEt/h .
We cannot determine a from the density-matrix formalism because is invariant under the trans-
formation |i ei |i, where is any real number.
7.9 Repeat the analysis of Problem 7.8 for spin-one particles coming on filters aligned successively
along +z, 45 from z towards x [i.e. along (1,0,1)], and along x.
Use classical electromagnetic theory to determine the outcome in the case that the spin-one
particles were photons and the filters were Polaroid. Why do you get a different answer?
Soln: Weadapt the calculation of Problem 7.8 by replacing the matrix for Jx by that for n J =
(Jx + Jz )/ 2. So if now (a, b, c) is | + ni in the usual basis, we have
b
1/2 1
a = 2 2
2 2 0 a a
12 0 1
2
b = b
1 1/2 b
0 2 c c c=
2
2+ 2
The normalisation yields b = 12 , so a = 21 /(2 2) and the required probability is the square of this,
0.25/(6 4 2) 0.73. So the probability of getting through all three filters is 31 (0.73)2 0.177.
In electromagnetism just one of two polarisations gets through the first filter, so we must say
that a photon has a probability of half of passing the first filter. Then we resolve
its E field along the
direction of the second filter and find that the amplitude of E falls by 1/ 2 on passing the second
filter, so half the energy and therefore photons that pass the first filter pass the second. Of these
just a half pass the third filter. Hence in total 81 = 0.125 of the photons get right through.
Although photons are spin-one particles, there are two major difference between the two cases.
Most obviously, polaroid selects for linear polarisation rather than circular polarisation, and a photon
with well-defined angular momentum is circularly polarised. The other difference is that a photon
can be in the state | + zi or | zi but not the state |0zi, where the z-axis is parallel to the photons
11
motion. This fact arises because emag waves are transverse so they do not drive motion in the
direction of propagation k; an angular momentum vector perpendicular to k would require motion
along k. Our theory does not allow for this case because it is non-relativistic, whereas a photon,
having zero rest mass, is an inherently relativistic object; we cannot transform to a frame in which
a photon is at rest so all three directions would be equivalent.
7.13 Write a computer program that determines the amplitudes am in
s
X
|n; s, si = am |s, mi
m=s
where n = (sin , 0, cos ) with any angle and |n; s, si is the ket that solves the equation (n
S)|n; s, si = s|n; s, si. Explain physically the nature of this state.
Use your am to evaluate the expectation values hSx i and Sx2 for this state and hence show
p
that the rms fluctuation in measurements of Sx will be s/2 cos .
Soln: We use a routine tridiag() that computes the e-values and e-kets of a real symmetric
tri-diagonal matrix the routine tqli() in Numerical Recipies by Press et al. is suitable.
#define J 100
#define NT 3
double tridiag(double*,double*,int,double**)// evaluates & ekets of real,
// symmetric tridiagonal matrix
double alphap(int j,int m){
if(m>=j)return 0;
return sqrt((double)(j*(j+1)-m*(m+1)));
}
double alpham(int j,int m){
if(m<=-j) return 0;
return sqrt((double)(j*(j+1)-m*(m-1)));
}
void expect(double *a,int j,double st){//evaluate <Sx> and <Sx2 >
double s1=0,s2=0;
for(int n=-j;n<=j;n++){
int nm2=n-2,nm1=n-1,np1=n+1,np2=n+2;
if(nm2>=-j) s2+=alpham(j,n)*alpham(j,nm1)*a[nm2]*a[n];
if(np2<=j) s2+=alphap(j,n)*alphap(j,np1)*a[np2]*a[n];
s2+=(alphap(j,nm1)*alpham(j,n)+alpham(j,np1)*alphap(j,n))*pow(a[n],2);
if(nm1>=-j) s1+=alpham(j,n)*a[nm1]*a[n];
if(np1<=j) s1+=alphap(j,n)*a[np1]*a[n];
}
s1*=.5; s2*=.25;
printf("%f %f %f %f\n",s1,j*st,s2,.5*j*(1-st*st)+pow(j*st,2));
}
int main(void){
double pi=acos(-1),theta[NT]={80, 120, 30};
double *D = new double[2*J+1];
double *E = new double[2*J+1];
double **Z = new double*[2*J+1];//allocate storage for square matrix
for(int i=0; i<2*J+1; i++) Z[i] = new double[2*J+1];
for(int it=0; it<3; it++){
theta[it]=theta[it]*pi/180;
double ct=cos(theta[it]), st=sin(theta[it]);
for(int m=-J; m<=J; m++){
D[J+m]=m*ct;//diagonal elements of matrix
if(m>-J) E[J+m]=st*.5*alpham(J,m);//sub-diagonal elements
}
tridiag(D,E,2*J+1,Z);//finds evalues & ekets of tridiagonal matrix
int mm;
for(int i=0; i<2*J+1; i++){
if(fabs(D[i]-J)<.05) mm=i; // identify eket m=J
12
}
expect(Z[mm]+J,J,st);
}
}
7.14 We have that
L+ Lx + iLy = ei + i cot . (7.1)
From the Hermitian nature of Lz = i/ we infer that derivative operators are anti-Hermitian.
So using the rule (AB) = B A on equation (7.1), we infer that
L L+ = +i cot ei .
This argument and the result it leads to is wrong. Obtain the correct result by integrating by parts
d sin d (f L+ g), where f and g are arbitrary functions of and . What is the fallacy in
R R
the given argument?
Soln:
g g
Z Z Z Z
d sin d (f L+ g) = d sin d f ei + i cot
g g
Z Z Z Z
i
= d e d sin f + i d cos d f ei
(sin f )
Z Z
= d ei [sin f g] d g
(f ei )
Z Z
i
+ i d cos [f e g] d g
The square brackets vanish so long f, g are periodic in . Differentiating out the products we get
f
Z Z Z Z Z
d sin d (f L+ g) = d ei d sin g + d cos gf
f
Z Z Z
i d cos d ei g + i d ei gf
The two integrals containing f g cancel as required leaving us with
f
Z
f
Z Z Z Z Z
i
d sin d (f L+ g) = d sin d ge + i cot = d sin d g(L f )
where
L = ei i cot .
The fallacy is the proposition that / is anti-Hermitian: the inclusion of the factor sin in the
integral prevents this being so.
7.15 By writing h2 L2 = (x p) (x p) = ijklm ijk xj pk ilm xl pm show that
P
2 L2
h 1
p2 = + 2 (r p)2 ihr p .
2
(7.2)
r r
By showing that p r r p = 2ih/r, obtain r p = rpr + ih. Hence obtain
2 L2
h
p2 = p2r + . (7.3)
r2
Give a physical interpretation of one over 2m times this equation.
13
Soln: From the formula for the product of two epsilon symbols we have
X
h2 L 2 =
(jl km jm kl )xj pk xl pm
jklm
X
= xj pk xj pk xj pk xk pj .
jk
= r2 p2 ihr p.
The second term is
X X
xj pk xk pj = xj (xk pk ih)pj
jk jk
X X
= xj (pj xk pk + ihjk pk ) 3ih xj pj
jk j
7.21 In this problem you show that many matrix elements of the position operator x vanish when
states of well-defined l, m are used as basis states. These results will lead to selection rules for electric
14
dipole radiation. First show that [L2 , xi ] = i jk jik (Lj xk + xk Lj ). Then show that L x = 0 and
P
using this result derive
X
[L2 , [L2 , xi ]] = i jik Lj [L2 , xk ] + [L2 , xk ]Lj = 2(L2 xi + xi L2 ).
(7.4)
jk
By squeezing this equation between angular-momentum eigenstates hl, m| and |l , m i show that
0 = ( )2 2( + ) hl, m|xi |l , m i,
where l(l + 1) and = l (l + 1). By equating the factor in front of hl, m|xi |l , m i to zero,
and treating the resulting equation as a quadratic equation for given , show that hl, m|xi |l , m i
must vanish unless l + l = 0 or l = l 1. Explain why the matrix element must also vanish when
l = l = 0.
Soln: X X X
[L2j , xi ] = (Lj [Lj , xi ] + [Lj , xi ]Lj ) = i jik (Lj xk + xk Lj )
j j jk
X X X
hL x = ijk xj pk xi = ijk (xj xi pk + xj [pk , xi ]) = ijk (xj xi pk ihxj ki )
ijk ijk ijk
P
Both terms on the right side of this expression involve ik ijk Sik where Sik = Ski so they vanish
by Problem 7.3. Hence x L = 0 as in classical physics.
Now
X X
[L , [L2 , xi ]] = i
2
jik [L2 , (Lj xk + xk Lj )] = i jik (Lj [L2 , xk ] + [L2 , xk ]Lj )
jk jk
X
= jik lkm (Lj {Ll xm + xm Ll } + {Ll xm + xm Ll }Lj )
jklm
X
= (jm il jl im )(Lj {Ll xm + xm Ll } + {Ll xm + xm Ll }Lj )
jlm
X
= (Lj {Li xj + xj Li } + {Li xj + xj Li }Lj Lj {Lj xi + xi Lj } {Lj xi + xi Lj }Lj )
j
X X
= (Lj Li xj + xj Li Lj ) L2 xi (Lj xi Lj + Lj xi Lj ) xi L2
j j
which implies
2 hlm|xi |l m i 2hlm|xi |l m i + hlm|xi |l m i 2 = 2hlm|xi |l m i + 2hlm|xi |l m i
Taking out the common factor we obtain the required result.
The quadratic for ( ) is
2 2( + 1) + ( 2) = 0
so p p
= + 1 ( + 1)2 ( 2) = + 1 4 + 1
p
= l (l + 1) + 1 4l2 + 4l + 1 = l (l + 1) + 1 (2l + 1)
= l2 + 3l + 2 or l2 l
We now have two quadratic equations to solve
l2 + l (l2 + 3l + 2) = 0 l = 12 [1 (2l + 3)]
l2 + l (l2 l ) = 0 l = 21 [1 (2l 1)]
Since l, l 0, the only acceptable solutions are l + l = 0 and l = l 1 as required. However, when
l = l = 0 the two states have the same (even) parity so the matrix element vanishes by the proof
given in eq (4.42) of the book.
7.22 Show that l excitations can be divided amongst the x, y or z oscillators of a three-dimensional
harmonic oscillator in ( 12 l + 1)(l + 1) ways. Verify in the case l = 4 that this agrees with the number
of states of well-defined angular momentum and the given energy.
Soln: If we assign nx of the l excitations to the x oscillator, we can assign 0, 1, . . . , lnx excitations
to the y oscillator [(l nx + 1) possibilities], and the remaining excitations go to z. So the number
of ways is
Xl Xl Xl
S (l nx + 1) = (l + 1) nx = (l + 1)2 21 l(l + 1) = (l + 1)( 21 l + 1)
nx =0 nx =0 nx =1
In the case of 4 excitations, the possible values of l are 4, 2 and 0, so the number of states is
(2 4 + 1) + (2 2 + 1) + 1 = 15, which is indeed equal to (4 + 1) (2 + 1).
7.23 Let
1 (l + 1)h
Al ipr + mr . (7.5)
2mh r
be the ladder operator of the three-dimensional harmonic oscillator and |E, li be the stationary state
of the oscillator that has energy E and angular-momentum
quantum number l. Show that if we
write Al |E, li = |E h, l + 1i, then = L l, where L is the angular-momentum quantum
number of a circular orbit of energy E. Show similarly that if Al1 |E, li = + |E + h, l 1i, then
+ = L l + 2.
Soln: Taking the mod-square of each side of Al |E, li = |E h, l + 1i we find
Hl E
| |2 = hE, l|Al Al |E, li = hE, L| (l + 32 ) |E, li = (l + 23 ).
h h
3
In the case l = L, | |2 = 0, so L = (E/
h) 2 and therefore | |2 = L l as required. We can
choose the phase of at our convenience.
Similarly
2+ = hE, l|Al1 Al1 |E, li = hE, l|(Al1 Al1 + [Al1 , Al1 ])|E, li
Hl1 1 Hl Hl1 E 1
= hE, l| (l + 2 ) + + 1 |E, li = l+ 2 =Ll+2
h
h h
16
7.24 Show that the probability distribution in radius of a particle that orbits in the three-
dimensional harmonic oscillator
p potential on a circular orbit with angular-momentum quantum
number l peaks at r/ = 2(l + 1), where
r
h
. (7.6)
2m
Derive the corresponding classical result.
Soln: The radial wavefunctions of circular orbits are annihilated by Al , so Al |E, li = 0. In the
position representation this is
1 l+1 r
+ + 2 u(r) = 0
r r r 2
Using the integrating factor,
Z
l r
= rl exp r2 /42 ,
exp dr + 2 (7.7)
r 2
2 2 2
/22
to solve the equation, we have u rl er /4 . The radial distribution is P (r) r2 |u|2 = r2(l+1) er .
Differentiating to find the maximum, we have
2(l + 1)r2l+1 r2(l+1) r/2 = 0 r = 2(l + 1)1/2 a
For the classical result we have
mv 2 lh
mrv = l h and = m 2 r r = v/ =
r mr
so r = (lh/m)1/2 = (2l)1/2 in agreement with the QM result when l 1.
7.25 A particle moves in the three-dimensional harmonic oscillator potential with the second
largest angular-momentum quantum number possible at its energy. Show that the radial wavefunc-
tion is r
l 2l + 1 x2 /4 h
u1 x x e where x r/ with . (7.8)
x 2m
How many radial nodes does this wavefunction have?
Soln: From Problem 7.24 we have that the wavefunction of the circular orbit with angular mo-
2 2
mentum l is hr|E, li rl er /4 . So the required radial wavefunction is
hr|E + h, l 1i hr|Al1 |E, li
rl+1 rl+1
l+1 r l r 2 /42 l1 l1 2 2
+ 2 re = lr + 2 (l + 1)r + 2 er /4
r r 2 2 2
2 2 r 2l + 1 2 2l + 1
= rl er /4 xl ex /4 x
2 r x
This wavefunction clearly has one node at x = 2l + 1.
7.28 The interaction between neighbouring spin-half atoms in a crystal is described by the Hamil-
tonian (1) (2)
(S(1) a)(S(2) a)
S S
H=K 3 , (7.9)
a a3
where K is a constant, a is the separation of the atoms and S(1) is the first atoms spin operator.
(1) (2) (1) (2) (1) (2)
Explain what physical idea underlies this form of H. Show that Sx Sx + Sy Sy = 21 (S+ S +
(1) (2)
S S+ ). Show that the mutual eigenkets of the total spin operators S 2 and Sz are also eigenstates
of H and find the corresponding eigenvalues.
At time t = 0 particle 1 has its spin parallel to a, while the other particles spin is antiparallel
to a. Find the time required for both spins to reverse their orientations.
17
Soln: This Hamiltonian recalls the mutual potential energy V of two classical magnetic dipoles
(i) that are separated by the vector a, which we can calculate by evaluating the magnetic field B
that the first dipole creates at the location of the second and then recognising that V = B.
(1) (2)
S+ S = (Sx(1) + iSy(1) )(Sx(2) iSy(2) ) = Sx(1) Sx(2) + Sy(1) Sy(2) + i(Sy(1) Sx(2) Sx(1) Sy(2) )
Similarly,
(1) (2)
S S+ = Sx(1) Sx(2) + Sy(1) Sy(2) i(Sy(1) Sx(2) Sx(1) Sy(2) )
Adding these expressions we obtain the desired relation.
We choose to orient the z-axis along a. Then H becomes
K 1 (1) (2) (1) (2)
H= 2 (S+ S + S S+ ) + Sz(1) Sz(2) 3Sz(1) Sz(2) . (7.10)
a
2
The eigenkets of S and Sz are the three spin-one kets |1, 1i, |1, 0i and |1, 1i and the single spin-zero
ket |0, 0i. We multiply each of these kets in turn by H:
K 1 (1) (2) (1) (2) (1) (2)
H|1, 1i = H|+i|+i = (S S + S S ) 2S S |+i|+i
a 2 + + z z
K
= |1, 1i
2a
(i)
which uses the fact that S+ |+i = 0. Similarly H|1, 1i = H|i|i = (K/2a)|1, 1i.
1 K 1 (1) (2) (1) (2) (1) (2)
H|1, 0i = H (|+i|i + |i|+i) = (S + S + S S + ) 2S z S z (|+i|i + |i|+i)
2 2a 2
K 1 K
= 2 + 1 (|+i|i + |i|+i) = a |1, 0i
2a
where we have used S+ |i = |+i, etc. Finally
1 K 1 (1) (2) (1) (2) (1) (2)
H|0, 0i = H (|+i|i |i|+i) = (S + S + S S + ) 2S z S z (|+i|i |i|+i)
2 2a 2
K
21 + 21 (|+i|i |i|+i) = 0
=
2a
The given initial condition
1
|i = |+i|i = (|1, 0i + |0, 0i),
2
which is a superposition of two stationary states of energies that differ by K/a. By analogy with the
symmetrical-well problem, we argue that after time h/E = ha/K the particle spins will have
reversed.
8.10 A spherical potential well is defined by
0 for r < a
V (r) = (8.1)
V0 otherwise,
where V0 > 0. Consider a stationary state with angular-momentum quantum number l. By writing
the wavefunction (x) = R(r)Ylm (, ) and using p2 = p2r + h2 L2 /r2 , show that the states radial
wavefunction R(r) must satisfy
2
h2 l(l + 1)h2
d 1
+ R+ R + V (r)R = ER. (8.2)
2m dr r 2mr2
Show that in terms of S(r) rR(r), this can be reduced to
d2 S S 2m
l(l + 1) 2 + 2 (E V )S = 0. (8.3)
dr2 r h
18
Assume that V0 > E > 0. For the case l = 0 write down solutions to this equation valid at (a) r < a
and (b) r > a. Ensure that R does not diverge at the origin. What conditions must S satisfy at
r = a? Show that these conditions can be simultaneously satisfied if and only if a solution can be
found to k cot ka = K, where h2 k2
= 2mE and h2 K 2 = 2m(V0 E). Show graphically that the
equation can only be solved when 2mV0 a/h > /2. Compare this result with that obtained for
the corresponding one-dimensional potential well.
The deuteron is a bound state of a proton and a neutron with zero angular momentum. Assume
that the strong force that binds them produces a sharp potential step of height V0 at interparticle
distance a = 2 1015 m. Determine in MeV the minimum value of V0 for the deuteron to exist.
Hint: remember to consider the dynamics of the reduced particle.
Soln: In the position representation pr = ih(/r + r1 ), so in this representation and for an
eigenfunction of L2 we get the required form of E|Ei = H|Ei = (p2 /2m + V )|Ei. Writing R = S/r
we have
2
1 d2 S
d 1 d 1 S 1 dS d 1 d 1 1 dS
+ R= + = + R= + =
dr r dr r r r dr dr r dr r r dr r dr2
Inserting this into our tise and multiplying through by r, we obtain the required expression.
When l = 0 the equation reduces to either exponential decay or shm, so with the given condition
on E we have
cos kr or sin kr at r < a
n
S
AeKr at r > a
2 2 2 2
where k = 2mE/ h and K = 2m(V0 E)/h . At r < a we must chose S sin kr because we
require R = S/r to be finite at the origin. We require S and its first derivative to be continuous at
r = a, so
sin(ka) = AeKa K p
Ka
cot(ka) = = W 2 /(ka)2 1
k cos(ka) = KAe k
q
with W 2mV0 a2 / h2 . In a plot of each side against ka, the right side starts at when ka = 0
and rises towards the x axis, where it terminates when ka = W . The left side starts at and
becomes negative when ka = /2. There is a solution iff the right side has not already terminated,
i.e. iff W > /2.
We obtain the minimum value of V0 for W = (a/h) 2mV0 = /2, so
h2
2 (h/a)2
V0 = = = 25.6 MeV
8ma2 4mp
where m 12 mp is the reduced mass of the proton.
q
8.13 From equation (8.50) show that l + 12 = (l + 12 )2 and that the increment in l when
l is increased by one satisfies 2 + (2l + 1) = 2(l + 1). By considering the amount by which the
solution of this equation changes when l changes from l as a result of increasing from zero to a
small number, show that
2
=1+ 2 + O( 2 ). (8.4)
4l 1
Explain the physical significance of this result.
Soln: The given eqn is a quadratic in l :
p
1 1 + 4l(l + 1) 4
q
l2 +l l(l +1)+ = 0 l = l + 12 = (l + 21 )2 , (8.5)
2
where weve chosen the root that makes l > 0.
Squaring up this equation, we have
(l + 21 )2 = (l + 12 )2 (l + + 21 )2 = (l + 23 )2
Taking the first eqn from the second yields
2 + 2(l + 12 ) = (l + 23 )2 (l + 12 )2 = 2(l + 1)
19
and that
4ih X
[Ni , (er )j ] [Nj , (er )i ] = ijt Lt (8.11)
r t
and hence that X
[Mi , Mj ] = 2ih2 mH ijk Lk . (8.12)
k
What physical implication does this equation have?
Soln: (a) Since Lc is a constant of motion
d V dV
(p Lc ) = p Lc = Lc = er Lc , (8.13)
dt x dr
where we have used Hamiltons equation p = H/x and r/x = er . Also
der
= er ,
dt
where = Lc /mr2 is the particles instantaneous angular velocity. So er Lc = mr2 er =
mr2 e r . Using this equation to eliminate er Lc from (8.13), we find that when dV /dr = Kr2 ,
the right side becomes mK e r , which is a total time-derivative, and the invariance of Mc follows.
Dotting Mc with Lc we find that Mc is perpendicular to Lc so it lies in the orbital plane. Also
Mc + mKer = p (r p) = p2 r p r p.
Evaluating the right side at pericentre, where p r = 0, we have
Mc = (p2 r mK)er .
In the case of a circular orbit, by centripetal balance p2 /mr = K/r2 and Mc = 0. At pericentre, the
particle is moving faster than the circular speed, so p2 > mK/r and the coefficient of er is positive,
so Mc points to pericentre.
(b) Since both p and L are Hermitian,
(p L)i =
X X
ijk (pj Lk ) = ijk Lk pj
jk jk
!
X X X
= ijk (pj Lk + [Lk , pj ]) = ijk pj L k + i kjm pm
jk jk m
= (p L)i 2ipi .
We want the RungeLenz vector to be a Hermitian operator, so we apply the principle that 12 (AB +
BA) is Hermitian even when [A, B] 6= 0 and write
X
Mi = 12
h ijk (pj Lk + Lk pj ) mKer = 21 h(p L L p) mKer
jk
M is a (pseudo) vector operator, so its components have the standard commutation relations with
the components of L.
(c) p2 is a scalar so it commutes with L, and of course it commutes with p, so it must commute
with both p L and L p. As a scalar 1/r commutes with L, so
ih 2 ih
[1/r, p L] = [1/r, p] L = [r , p] L = 3 x L.
2r3 r
Similarly,
1
[1/r, L p] = ihL x .
r3
21
Now
1 X 1 X 1X
(x L)i = ijk klm xj xl pm = ijk lmk xj xl pm = (il jm im jl )xj xl pm
h
h
h
jklm jklm jlm
1
= (xi x p r2 pi )
h
and
1 X 1 X 1X
(L x)i = ijk jlm xl pm xk = jki jlm xl pm xk = (kl im km il )xl pm xk
h
h
h
jklm jklm klm
1X 1X
= (xk pi xk xi pk xk ) = (pi xk xk + ihik xk pk xi xk ihki xk )
h
h
k k
1
pi r2 p x xi
=
h
Hence
n 1 1
[1/r, N] = [p L, 1/r] [L p, 1/r] = i 3 (xi x p r2 pi ) + pi r2 p x xi 3 } (8.14)
r r
(d)
X
[p2 , (er )n ] = [p2 , xn /r] = (pj [pj , xn /r] + [pj , xn /r]pj )
j
X
= (pj [pj , xn ]/r + pj xn [pj , 1/r] + [pj , xn ]/rpj + xn [pj , 1/r]pj )
j
X jn xj jn xj
= ih pj + pj xn 3 pj + xn 3 pj
j
r r r r
X
1 1 xj xj
= ih pn + pn + pj 3 xn + xn 3 pj
r r j
r r
(e)
p2
K
[H, M] = , 12 h{p L L p} mKer
2m r
The results we have in hand imply that when we expand this commutator, there are only two
non-zero terms, so
1
[H, M] = 21 K p2 , er 21
hK , p L L p
r
X
1 1 xj xj 1 1
= 12 ihK pj 3 x + x 3 pj + 3 x x p r2 p pr2 p x x 3
p + p
r r j
r r r r
=0
This result shows: (i) that the eigenvalues of the Mi are good quantum numbers if the particle
starts in an eigenstate of Mi , it will remain in that state; (ii) the unitary transformations Ui ()
exp(iMi ) are dynamical symmetries of a hydrogen atom. In particular, these operators turn
stationary states into other stationary states of the same energy.
(f) (i)
X X X
[Mi , L2 ] = [Mi , L2j ] = ([Mi , Lj ]Lj + Lj [Mi , Lj ]) = i ijk (Mk Lj + Lj Mk ) 6= 0.
j j jk
so we do not expect to know the total angular momentum when the atom is in an eigenstate of any
of the Mi .
22
(ii) [Li , M 2 ] = 2
P P
j [Li , Mj ] = i jk ijk (Mk Mj + Mj Mk ) = 0, so there is a complete set of
mutual eigenstates of L2 , Lz and M 2 .
(g)
X X X X
[(p L)i , pm ] = ijk [pj Lk , pm ] = ijk pj [Lk , pm ] = i ijk kmn pj pn = i kij kmn pj pn
jk jk jkn jkn
X
2
=i (im jn in jm )pj pn = i(p im pi pm )
nj
= pi (p L)s (L p)s pi
(8.16)
The standardised sum of cross products in equation (8.15) is now
i 2pi (p L)s + 2(L p)s pi + pi (p L)s + pi (p L)s (L p)s pi (L p)s pi
and is manifestly zero. The last term in (8.15) has to vanish because it alone is symmetric in is,
and its not hard to show that it does:
X
pN+Np= ijk pi (pj Lk Lj pk ) + (pj Lk Lj pk )pi
ijk
The first and last terms trivially vanish because they are symmetric in ij and ik,respectively. The
remaining terms can be written
X X
ijk pi Lj pk + ijk pj Lk pi
ijk jki
23
Hence
7 2 9
h a /2m + 12 m 2 32
32
1 5
a 2 7 2
h 1 2 2
hHi = 5 7 = a + 10 m a
32 a 2m 5
26
hHi h2
0= = 57 a3 + 15 m 2 a
a m
2
h
7
a4 = 7 a = 71/4 2 hHi =
h
m 5
2 2
10.14 Using the result proved in Problem 10.13, show that the trial wavefunction b = eb r /2
yields 8/(3)R as an estimate of hydrogens ground-state energy, where R is the Rydberg constant.
2 2 2 2
Soln: With = eb r /2 , d/dr = b2 reb r /2 , so
2 4Z ,Z
h b
e2
Z
4 b2 r 2 b2 r 2 2 2
hHi = dr r e dr re dr r2 eb r
2m 40
2 Z , Z
h
e2 1
Z
4 x2 x2 2
= dx x e dx xe dx x2 ex
2mb 40 b2 b3
Now " #
2
ex
Z
x2
dx xe = = 21
2
0
"
x2
#
xe
Z Z
2
x2
dx x2 ex = 1
+ 2 dx e =
2 4
" #0
3 x2
x e 3
Z Z
2 2
dx x4 ex = + 23 dx x2 ex =
2 8
0
so ,
h2 3 e2 1 h2 b2 e2 b
3
hHi = 2 2 3
= 3/2
2mb 8 40 b 4b 4m 2 0
At the stationary point of hHi b = me2 /(3 3/2 0 h2 ). Plugging this into hHi we find
2 2
h2 m2 e4
3 e2 me2 8 m e 8
hHi = 4 3/2 2 = 3 2 = R
4m 9 3 20
h 2 0 3 3/2 0 h 4 0 3
10.18 A particle of mass m is initially trapped by the well with potential V (x) = V (x),
where V > 0. From t = 0 it is disturbed by the time-dependent potential v(x, t) = F xeit . Its
subsequent wavefunction can be written
Z
iE0 t/
h
|i = a(t)e |0i + dk {bk (t)|k, ei + ck (t)|k, oi} eiEk t/h , (10.2)
where E0 is the energy of the bound state |0i and Ek h2 k 2 /2m and |k, ei and |k, oi are, respectively
the even- and odd-parity states of energy Ek (see Problem 5.17). Obtain the equations of motion
Z
ih a|0ie
iE0 t/
h
+ dk b k |k, ei + ck |k, oi eiEk t/h
Z (10.3)
= v a|0ieiE0 t/h + dk (bk |k, ei + ck |k, oi) eiEk t/h .
Given that the free states are normalised such that hk , o|k, oi = (k k ), show that to first order
in v, bk = 0 for all t, and that
iF sin(k t/2) Ek E0
ck (t) = hk, o|x|0i eik t/2 , where k . (10.4)
h
k /2 h
Hence show that at late times the probability that the particle has become free is
2mF 2 t |hk, o|x|0i|2
Pfr (t) = . (10.5)
h3 k
k =0
27
4K 2 =
The required result follows when we substitute into the above k 2 /K 2 = Ef /|E0 | and h
2
(2mE0 ) .
28
11.4 In terms of the position vectors x , x1 and x2 of the particle and two electrons, the centre
of mass and relative coordinates of a helium atom are
m x + me (x1 + x2 )
X , r1 x1 X, r2 x2 X, (11.1)
mt
where mt m + 2me . Write the atoms potential energy operator in terms of the ri .
Show that
= + +
X x x1 x2
(11.2)
me me
= =
r1 x1 m x r2 x2 m x
and hence that the kinetic energy operator of the helium atom can be written
2
h2 2 h2 2 2 h2
K = + 2 , (11.3)
2mt X2 2 r21 r2 2mt x1 x2
where me (1 + 2me /m ). What is the physical interpretation of the third term on the right?
Explain why it is reasonable to neglect this term.
Soln: We have from the definitions
x1 = X + r1 x2 = X + r2
1 1
x = (mt X me (x1 + x2 )) = (mt X me (2X + r1 + r2 ))
m m
me
=X (r1 + r2 )
m
Directly computing the differences xi x , etc, one finds easily that
e2
2 2 1
V = + .
40 |r1 + (me /m )(r1 + r2 )| |r1 + (me /m )(r1 + r2 )| |r1 r2 |
By the chain rule
x x1 x2
= + + = + +
X X x X x1 X x2 x x1 x2
as required. Similarly
x x1 me
= + = +
r1 r1 x r1 x1 m x x1
and similarly for /r2 . Squaring these expressions, we have
2
2 2
= + 2 + + +
X2 x2 x x1 x2 x1 x2
2 m2e 2 me 2 2
= 2 2 +
r21 m x2 m x1 x x21
2 m2 2 me 2 2
2 = 2e 2 +
r2 m x 2 m x2 x x22
If we add the first of these eqns to m /me times the sum of the other two, the mixed derivatives in
x cancel and we are left with
2 m 2 2
2 2
2 2
me m
2
+ 2 + 2 = 1 + 2 2
+ 1 + 2 + 2 +2
X me r1 r2 m x me x1 x2 x1 x2
Dividing through by mt we obtain
1 2
2
2 1 2
2
2 2
m 1 me 2
+ + = + 1 + +
mt X2 me mt r21 r22 m x2 me mt x21 x22 mt x1 x2
After multiplication by h2 /2 the first term on the right and the unity part of the second term
constitute the atoms KE operator. So we transfer the remaining terms to the left side and have the
stated result.
The final term in K must represent the kinetic energy that the -particle has as it moves around
the centre of mass in reflex to the faster motion of the electrons. It will be smaller than the double
derivatives with respect to ri by at least a factor me /m . (Classically wed expect the velocities to
be smaller by this factor and therefore the kinetic energies to be in the ratio m2e /m2 .)
31
11.7 Assume that a LiH molecule comprises a Li+ ion electrostatically bound to an H ion, and
that in the molecules ground state the kinetic energies of the ions can be neglected. Let the centres
of the two ions be separated by a distance b and calculate the resulting electrostatic binding energy
under the assumption that they attract like point charges. Given that the ionisation energy of Li
is 0.40R and using the result of Problem 11.6, show that the molecule has less energy than that of
well separated hydrogen and lithium atoms for b < 4.4a0 . Does this calculation suggest that LiH is
a stable molecule? Is it safe to neglect the kinetic energies of the ions within the molecule?
Soln: When the LI and H are well separated, the energy required to strip an electron from the Li
and park it on the H is E = (0.4 + 1 0.955)R = 0.445R. Now we recover some of this energy
by letting the Li+ and H fall towards each other. When they have reached distance b the energy
released is
e2 a0
= 2R
40 b b
This energy equals our original outlay when b = (2/0.445)a0 = 4.49a0, which establishes the required
proposition.
In LiH the Li-H separation will be < 2a0 , because only at a radius of this order will the electron
clouds of the two ions generate sufficient repulsion to balance the electrostatic attraction we have
been calculating. At this separation the energy will be decidedly less than that of isolated Li and
H, so yes the molecule will be stable.
In its ground state the molecule will have zero angular momentum, so there is no rotational
kinetic energy to worry about. However the length of the Li-H bond will oscillate around its equi-
librium value, roughly as a harmonic oscillator, so there will be zero-point energy. However, this
energy will suffice only to extend the bond length by a fraction of its equilibrium value, so it does
not endanger the stability of the molecule.
11.8 Two spin-one gyros are in a box. Express the states |j, mi in which the box has definite
angular momentum as linear combinations of the states |1, mi|1, m i in which the individual gyros
have definite angular momentum. Hence show that
1
|0, 0i = (|1, 1i|1, 1i |1, 0i|1, 0i + |1, 1i|1, 1i). (11.4)
3
By considering the symmetries of your expressions, explain why the ground state of carbon has l = 1
rather than l = 2 or 0. What is the total spin angular momentum of aC atom?
Soln: We have that J |2, 2i = 2|2, 1i, J |2, 1i = 6|2, 0i, J |1, 1i = 2|1, 0i, J |1, 0i = 2|1, 1i.
We start from
|2, 2i = |1, 1i|1, 1i
and apply J to both sides, obtaining
1
2|2, 1i = 2(|1, 0i|1, 1i + |1, 1i|1, 0i) |2, 1i = (|1, 0i|1, 1i + |1, 1i|1, 0i)
2
Applying J again we find
1
|2, 0i = (|1, 1i|1, 1i + 2|1, 0i|1, 0i + |1, 1i|1, 1i)
6
Next we identify |1, 1i as the linear combination of |1, 1i|1, 0i and |1, 0i|1, 1i thats orthogonal to
|2, 1i. It clearly is
1
|1, 1i = (|1, 0i|1, 1i |1, 1i|1, 0i)
2
We obtain |1, 0i by applying J to this
1
|1, 0i = (|1, 1i|1, 1i |1, 1i|1, 1i)
2
and applying J again we have
1
|1, 1i = (|1, 1i|1, 0i |1, 0i|1, 1i)
2
32
Finally we have that |0, 0i is the linear combination of |1, 1i|1, 1i, |1, 1i|1, 1i and |1, 0i|1, 0i thats
orthogonal to both |2, 0i and |1, 0i. By inspection its the given expression.
The kets for j = 2 and j = 0 are symmetric under interchange of the m values of the gyros,
while that for j = 1 is antisymmetric under interchange. Carbon has two valence electrons both in
an l = 1 state, so each electron maps to a gyro and the box to the atom. When the atom is in the
|1, 1i state, for example, from the above the part of the wavefunction that described the locations
of the two valence electrons is
1
hx1 , x2 |1, 1i = (hx1 |1, 0ihx2 |1, 1i hx1 |1, 1ihx2 |1, 0i)
2
This function is antisymmetric in its arguments so vanishes when x1 = x2 . Hence in this state of
the atom, the electrons do a good job of keeping out of each others way and we can expect the
electron-electron repulsion to make this state (and the other two l = 1 states) lower-lying than the
l = 2 or l = 0 states, which lead to wavefunctions that are symmetric functions of x1 and x2 .
Since the wavefunction has to be antisymmetric overall, for the l = 1 state it must be symmetric
in the spins of the electrons, so the total spin has to be 1.
11.9 Suppose we have three spin-one gyros in a box. Express the state |0, 0i of the box in which
it has no angular momentum as a linear combination of the states |1, mi|1, m i|1, m i in which the
individual gyros have well-defined angular momenta. Hint: start with just two gyros in the box,
giving states |j, mi of the box, and argue that only for a single value of j will it be possible to get
|0, 0i by adding the third gyro; use results from Problem 11.8.
Explain the relevance of your result to the fact that the ground state of nitrogen has l = 0.
Deduce the value of the total electron spin of an N atom.
Soln: Since when we add gyros with spins j1 and j2 the resulting j satisfies |j1 j2 | j j1 + j2 ,
we will be able to construct the state |0, 0i on adding the third gyro to the box, only if the box has
j = 1 before adding the last gyro. From Problem 11.8 we have that
1
|0, 0i = (|1, 1i|1, 1i |1, 0i|1, 0i + |1, 1i|1, 1i),
3
where we can consider the first ket in each product is for the combination of 2 gyros and the second
ket is for the third gyro. We use Problem 11.8 again to express the kets of the 2-gyro box as linear
combinations of the kets of individual gyros:
1 1 1
|0, 0i = |1, 1i|1, 0i |1, 0i|1, 1i |1, 1i |1, 1i|1, 1i |1, 1i|1, 1i |1, 0i
3 2 2
1
+ |1, 0i|1, 1i |1, 1i|1, 0i |1, 1i ,
2
1
= |1, 1i|1, 0i|1, 1i |1, 0i|1, 1i|1, 1i |1, 1i|1, 1i|1, 0i
6
+ |1, 1i|1, 1i|1, 0i + |1, 0i|1, 1i|1, 0i |1, 1i|1, 0i|1, 0i
This state is totally antisymmetric under exchange of the m values of the gyros.
When we interpret the gyros as electrons and move to the position representation we find that
the wavefunction of the valence electrons is a totally antisymmetric function of their coordinates,
x1 , x2 , x3 . Hence the electrons do an excellent job of keeping out of each others way, and this will
be the ground state. To be totally antisymmetric overall, the state must be symmetric in the spin
labels of the electrons, so the spin states will be |+i|+i|+i and the states obtained from this by
application of J . Thus the total spin will be s = 32 .
11.10 Consider a system made of three spin-half particles with individual spin states |i. Write
down a linear combination of states such as |+i|+i|i (with two spins up and one down) that is
symmetric under any exchange of spin eigenvalues . Write down three other totally symmetric
states and say what total spin your states correspond to.
Show that it is not possible to construct a linear combination of products of |i which is totally
antisymmetric.
What consequences do these results have for the structure of atoms such as nitrogen that have
three valence electrons?
33
Soln: There are just three of these product states to consider because there are just three places
to put the single minus sign. The sum of these states is obviously totally symmetric:
1
|i = |+i|+i|i + |+i|i|+i + |i|+i|+i
3
Three other totally symmetric state are clearly |+i|+i|+i and what you get from this ket and the
one given by everywhere interchanging + and . These four kets are the kets | 32 , mi.
A totally antisymmetric state would have to be constructed from the same three basis kets used
above, so we write it as
| i = a|+i|+i|i + b|+i|i|+i + c|i|+i|+i
On swapping the spins of the first and the third particles, the first and third kets would interchange,
and this would have to generate a change of sign. So a = c and b = 0. Similarly, by swapping the
spins on the first and second particles, we can show that a = 0. Hence |i = 0, and we have shown
that no nonzero ket has the required symmetry.
States that satisfy the exchange principle can be constructed by multiplying a spatial wave-
function that is totally antisymmetric in its arguments by a totally symmetric spin function. Such
states have maximum total spin. In contrast to the situation with helium, conforming states can-
not be analogously constructed by multiplying a symmetric wavefunction by an antisymmetric spin
function.
11.11 In this problem we use the variational principle to estimate the energies of the singlet and
triplet states 1s2s of helium by refining the working of Appendix K.
The idea is to use as the trial wavefunction symmetrised products of the 1s and 2s hydrogenic
wavefunctions (Table 8.1) with the scale length aZ replaced by a1 in the 1s wavefunction and by a
different length a2 in the 2s wavefunction. Explain physically why with this choice of wavefunction
we expect hHi to be minimised with a1 0.5a0 but a2 distinctly larger.
Using the scaling properties of the expectation values of the kinetic-energy and potential-energy
operators, show that
2
a20
a0 4a0 a0
hHi = + 2 + 2a0 (D(a1 , a2 ) E(a1 , a2 )) R,
a21 a1 4a2 a2
where D and E are the direct and exchange integrals.
Show that the direct integral can be written
Z
2 1
dx x2 e2x 8 (8 + 6y + 2y 2 + y 3 )ey ,
D=
a2 0 4y
where x r1 /a1 and y = r1 /a2 . Hence show that with 1 + 2a2 /a1 we have
a2 4
1 6 6 12
D= 1 22 + + + .
a1 a1 2 3 4 5
Show that with y = r1 /a2 and = r2 /2a2 the exchange integral is
2
Z
E= d3 x1 0 0
10 (x1 )20 (x1 )
(a1 a2 )3/2
3 Z y/2 2 Z
1 2a2 2a2
d (2 3 /)e + d ( 2 /)e .
r1 0 y/2
Using
Z b
d (2 3 /)e = [{(1 3 )(2 + 2 + 2 ) 1 3 }e ]ba
a
and Z b
d ( 2 /)e = [{(1 2 )(1 + ) 1 2 }e ]ba
a
34
show that Z
2 2 r1
E= dr1 r1 1 er1 /2a2
(a1 a2 )3 0 2a2
3 h
1 2a2 i
2(1 3 ) {(1 3 )(2 + y + 41 2 y 2 ) 18 2 y 3 }ey/2
r1
2
2a2 2 1 1 2 y/2
+ {(1 )(1 + 2 y) 4 y }e
8a2
50 66
= 5 23 10 + 2 ,
a1
Using the above results, show numerically that the minimum of hHi occurs near a1 = 0.5a0 and
a2 = 0.8a0 in both the singlet and triplet cases. Show that for the triplet the minimum is 60.11 eV
and for the singlet it is 57.0 eV. Compare these results with the experimental values and the values
obtained in Appendix K.
Soln: Wed expect the 2s electron to see a smaller nuclear charge than the 1s electron and therefore
to have a longer scale length since the latter scales inversely with the nuclear charge.
The 1s orbit taken on its own has K = (a0 /a1 )2 R because the kinetic energy is R for hydrogen
and it is proportional to the inverse square of the wavefunctions scale length. The 1s potential
energy is W = 4(a0 /a1 )R because in hydrogen it is 2R, and its proportional to the nuclear
charge and to the inverse of the wavefunctions scale length. Similarly, the 2s orbit taken on its
own has K = 41 (a0 /a2 )2 R and W = (a0 /a2 )R, both just 14 of the 1s values from the 1/n2 in the
Rydberg formula. The electron-electron energies are (D E)2a0 R because R = e2 /80 a0 . The
required expression for hHi now follows.
When the scale length aZ is relabelled a1 where it relates to the 1s electron and is relabelled a2
where it relates to the 2s electron, equation (K.2) remains valid with redefined to r2 /a2 and x
replaced by y r1 /a2 . With these definitions the first line of equation (K.2) remains valid and the
second line becomes Z
2 1
dx x2 e2x 8 (8 + 6y + 2y 2 + y 3 )ey
D=
a2 0 4y
Z Z (11.5)
x2
1 x
= 8 dx x e2x dx 2 (8y + 6y 2 + 2y 3 + y 4 )e(2x+y)
2a2 0 y 0 y
R n y (n+1)
Now x/y = a2 /a1 and 0 dy y e = n! so with 1 + 2a2 /a1 we have
3
1 a2 a 8 6 2 1
D= 2 23 + 2! + 3! + 4!
2a2 a1 a1 2 3 4 5
(11.6)
a22 4
1 6 6 12
= 1 2 + 3+ 4+ 5
a1 a1 2
which agrees with equation (K.2) when a1 = a2 = aZ as it should.
Equation (K.3) for the exchange integral becomes
1
Z
E= d3 x1 0 0
10 (x1 )20 (x1 )
2(a1 a2 )3/2
(11.7)
r2 (1 r2 /2a2 ) sin 2 er2 /2a2
Z
dr2 d2 2 p 2 .
|r1 + r22 2r1 r2 cos 2 |
After integrating over as in Box 11.1, we have
2
Z
E= d3 x1 0 0
10 (x1 )20 (x1 )
(a1 a2 )3/2
Z r1 Z
r22
r2 r2 /2a2 r2 r2 /2a2
dr2 1 e + dr2 r2 1 e
0 r1 2a2 r1 2a2
35
Figure 11.4 Estimates of the energy in electron volts of the 1s2s triplet excited state of helium. The estimates
are obtained by taking the expectation of the Hamiltonian using anti-symmetrised products of 1s and 2s hydrogenic
wavefunctions that have scale lengths a1 and a2 , respectively.
8a2 16
2 6
E = 2 23 1 3 1 2 (1 3 ) 4 12 (1 2
2
) + ( 4 1) 3 (1 2
3
) + 21 4 (1 4
a1 3 2 )
2
8a
= 5 23 16 1 3 1 2 4(1 3 )(1 1 ) + ( 4 1)(2 3 ) + 3 (1 2 )
a1
8a2
50 66
= 5 23 10 + 2 ,
a1