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Approximations

We intend now to extend the reach of quantum mechanics beyond the

soluble problems we have treated so far. The most useful method for do-

ing this is perturbation theory, which starts from the assumption that the

Hamiltonian H diﬀers from a soluble Hamiltonian H

0

by the addition of

a term V that is small. In the time-independent form of the theory, best

suited to problems with a discrete energy spectrum, V must be small com-

pared to the energy diﬀerences between the unperturbed states. In the time

dependent case, useful for problems where there is a continuum of energy

states, the product V t/ must be much less than unity. In both forms, the

solution is obtained by expanding both eigenvalues and eigenfunctions in a

series in a small parameter that represents the strength of the perturbing

term. Care must be taken in time-independent perturbation theory if the

unperturbed state is part of a degenerate set. In addition to perturbation

theory, we will also discuss the variational method.

1.1 Time-independent Perturbation Theory

Let the Hamiltonian be H = H

0

+ V , and let the eigenstates and eigen-

values of H

0

be known:

H

0

[φ

n

` =

n

[φ

n

`. (1.1)

Let the eigenstates of H

0

constitute a complete orthonormal set and let

the energy spectrum be discrete. The eigenstates of the full Hamiltonian

H and the corresponding eigenvalues are expanded in a series of increasing

powers of the perturbing potential V (or of some parameter involved in it

1

multiplicatively):

[ψ

n

` = [φ

n

` +[ψ

(1)

n

` +[ψ

(2)

n

` + ... (1.2)

E

n

=

n

+ E

(1)

n

+ E

(2)

n

+ ... (1.3)

Superscripts in parentheses indicate the power of V to which the term is

proportional, the order of the term. In Eq.(1.2) it can be assumed without

loss of generality that the higher order corrections [ψ

(p)

n

` are orthogonal to

the unperturbed state [φ

n

`. If this is not true initially, the corrections to

the state can be expanded in terms of the unperturbed eigenstates, and the

terms involving [φ

n

` can moved to the left and combined with the [φ

n

` term

in the expansion. The remaining terms are all orthogonal to [φ

n

`. As a

result of this operation, the coeﬃcient of [φ

n

` on the right of Eq.(1.2) is

no longer unity. The state can be renormalized, however, by dividing by

this coeﬃcient leaving an expansion of the given form with all corrections

orthogonal to the unperturbed state.

If Eqs.(1.2) and (1.3) are substituted into the eigenvalue equation H[ψ

n

` =

E

n

[ψ

n

` and the terms of same order equated, we obtain

H

0

[φ

n

` =

n

[φ

n

`, (1.4)

H

0

[ψ

(1)

n

` + V [φ

n

` = E

(

n

1)[φ

n

` +

n

[ψ

(1)

n

`, (1.5)

H

0

[ψ

(2)

n

` + V [ψ

(1)

n

` = E

(2)

n

[φ

n

` + E

(1)

n

[ψ

(1)

n

` +

n

[ψ

(2)

n

`, (1.6)

and equations of higher order. The ﬁrst equation is of zero order in V

and aﬃrms that the unperturbed state is an eigenstate of the unperturbed

Hamiltonian. The ﬁrst order corrections to the energy and the state are

determined by Eq.(1.5). Take its inner product with 'φ

n

[ to get

'φ

n

[V [φ

n

` = E

(1)

n

(1.7)

The second term on the right of Eq.(1.5) makes no contribution because of

the orthogonality of the higher corrections to the unperturbed state. The

ﬁrst term on the left is 'φ

n

[H

0

[ψ

(1)

n

` = 'ψ

(1)

n

[H

0

[φ

n

`

∗

= 'ψ

(1)

n

[

n

[φ

n

`

∗

, which

vanishes for the same reason. Eq.(1.7) says that the ﬁrst order correction

to the energy is the expectation value of the perturbing potential in the

unperturbed state. The ﬁrst order correction to the state is found by taking

the inner product of Eq.(1.5 with 'φ

m

[ with m = n. The ﬁrst term in the

left is 'φ

m

[H

0

[ψ

(1)

n

` = 'ψ

(1)

n

[H

0

[φ

m

`

∗

=

m

'φ

m

[ψ

(1)

n

`, and the ﬁrst term on

the right is zero by orthogonality. The resulting equation can be solved for

'φ

m

[ψ

(1)

n

`:

'φ

m

[ψ

(1)

n

` =

'φ

m

[V [φ

n

`

n

−

m

,

2

from which the expansion of the ﬁrst order correction can be constructed as

[ψ

(1)

n

` =

¸

m=n

[φ

m

`'φ

m

[ψ

(1)

n

` =

¸

m=n

[φ

m

`

'φ

m

[V [φ

n

`

n

−

m

(1.8)

If one or more of the states [φ

m

` is degenerate with the unperturbed state,

the denominator in the last equation vanishes and Eq.(1.8) becomes mean-

ingless. We will return to this problem of degenerate perturbations later,

and proceed now assuming no degeneracy.

Perturbation theory can be carried to any order in principle, but it be-

comes more and more involved as the order increases. Here we will go only

to ﬁrst order in the state and second order in the energy where the results

are simple enough to be useful. The inner product of 'φ

n

[ with the second

order equation (1.6) above yields 'φ

n

[V [ψ

(1)

n

` = E

(2)

n

. Contributions from

the ﬁrst term on the left and the second and third terms on the right are

zero by the same arguments as before. Using Eq.(1.8) we ﬁnd

E

(2)

n

=

¸

m

'φ

n

[V [φ

m

`'φ

m

[V [φ

n

`

n

−

m

=

¸

m

['φ

n

[V [φ

m

`[

2

n

−

m

(1.9)

As an example of the application of non-degenerate perturbation theory,

we consider a charged harmonic oscillator perturbed by an electric ﬁeld. The

unperturbed Hamiltonian is H

0

= (a

†

a+

1

2

)ω, its eigenvalues are (n+

1

2

)ω,

and its eigenstates will be denoted by [n`. The perturbing potential is

V = −ecx = −(ec/

√

2)(a

†

+ a). To construct the matrix elements of V

that enter the perturbation formulas, we let V act on an unperturbed state:

V [n` = −

ec

√

2

√

n + 1 [n + 1` +

√

n[n −1`

.

From this equation we obtain the ﬁrst and second order corrections to the

energy:

E

(1)

n

= 'n[V [n`

= 0

E

(2)

n

=

¸

m=n

['m[V [n`[

2

n

−

m

=

1

2

e

2

c

2

2

(n + 1)

−ω

+

1

2

e

2

c

2

2

n

ω

= −

e

2

c

2

2

2ω

3

Thus the second order perturbation theory result for the energy of the n-th

state is E

n

= (n+

1

2

)ω − (e

2

c

2

2

/2ω). The eigenstate [ψ

n

` correct to ﬁrst

order is given by Eq.(1.8), which in this case takes the form

[ψ

n

` = [n` −

1

2

e

2

c

2

2

(n + 1)

ω

[n + 1` +

1

2

e

2

c

2

2

n

ω

[n −1`.

The physical interpretation of the added corrections can be seen by reex-

pressing this equation in wave function form and plotting the resulting wave

patterns. The eﬀect is to shift the wave function slightly in the direction

of the electric force, so that the charge distribution is no longer centered at

the origin. Thus the electric ﬁeld induces an electrice dipole moment with

respect to the origin. The energy shift represents the interaction of the in-

duced dipole moment with the ﬁeld. It is quadratic in the ﬁeld because the

induced moment is proportional to the ﬁeld and the energy is the product

of the ﬁeld with the moment.

Here because of the special properties of the harmonic oscillator, the sum

involved in the second order eigenvalue and the ﬁrst order eigenstate contain

only two terms. Normally the series would be inﬁnite, and would have to be

evaluated numerically. Another special harmonic oscillator feature is that

the energy correction is a constant independent of the unperturbed state, so

that the energy levels remain equally spaced. The physical reason for this

is that the eﬀect of the electric ﬁeld, like the eﬀect of gravity on a hanging

spring, is to shift the equilibrium point and the equilibrium energy without

aﬀecting the frequency of oscillation. The perturbed system is still an os-

cillator of frequency ω. In fact, this example is only intended to illustrate

the workings of perturbation theory, because the full Hamiltonian is exactly

soluble. This and other examples of the application of perturbation theory

to non-degenerate states are left to the problems.

The singular denominators that cause diﬃculties in the degenerate case

can be avoided by choosing the basis states properly. A set of n degenerate

eigenstates is not unique because any orthonormal set of n independent

linear combinations of the original set is also a set of degenerate states with

the same energy eigenvalue. We can use this freedom of choice to eliminate

the oﬀ-diagonal elements of the matrix representing V within the degenerate

set and thereby eliminate the oﬀending terms in Eqs.(1.8) and (1.9). The

oﬀ-diagonal elements can be made to vanish by choosing the eigenstates of V

within the degenerate set as a new set of unperturbed states. With the oﬀ-

diagonal elements eliminated, the ﬁrst order corrections to the state Eq.(1.8)

and the second order corrections to the energy Eq.(1.9) come only from

states which are not degenerate with the unperturbed state. No vanishing

4

denominators occur. Eq.(1.7) then tells us that the ﬁrst order corrections

to the energy are the diagonal elements of V in the new basis.

The procedure is best explained by an example. Consider an isotropic

harmonic oscillator in two dimensions perturbed by a potential V = γxy.

The unperturbed eigenvalues (n

x

+ n

y

+ 1)ω are degenerate. Denote the

eigenstates by [n

x

n

y

`. Consider the eﬀect of the perturbation on the second

excited state, which comprises the threefold degenerate set [20`, [11`, and [02`.

The action of V on each of the basis states is easily calculated by expressing

V in terms of the raising and lowering operators as γ(

2

/2)(a

†

x

+a

x

)(a

†

y

+a

y

):

V [20` =

γ

2

2

√

3[31` +

√

2[11`

, (1.10)

V [11` =

γ

2

2

2[22` +

√

2[20` +

√

2[02` +[00`

, (1.11)

V [02` =

γ

2

2

√

3[13` +

√

2[11`

. (1.12)

The operator V results in states both inside and outside the degenerate set.

To ﬁnd the ﬁrst order energy corrections, we need the matrix representing

V within the degenerate set:

V =

γ

2

√

2

¸

0 1 0

1 0 1

0 1 0

¸

(1.13)

The eigenvalues are 0, γ

2

, and −γ

2

and the corresponding normalized

eigenstates are

[φ

1

` =

¸

1

2

0

−

1

2

¸

, [φ

2

` =

¸

1

2

1

2

1

2

¸

, [φ

3

` =

¸

1

2

−

1

2

1

2

¸

. (1.14)

These are the ﬁrst order energies and the new unperturbed eignestates.

Using the new states as a basis, the matrix representing V takes the form

V = γ

2

¸

0 0 0

0 1 0

0 0 −1

¸

**with no oﬀ-diagonal elements. First order corrections to the state and second
**

order corrections to the energy will involve only the states [31`, [22`, [13`,

and [00` that appear on the right side of Eqs. (1.10)-(1.12). Matrix elements

of V that would add other states are zero. These correction to the energy

and state involve ﬁnite sums. Detailed calculation of these corrections is

omitted.

5

1.2 The Stark Eﬀect in Hydrogen

The importance of symmetry in the application of perturbation theory to

problems involving degeneracy is illustrated in the calculation of the eﬀect

of an electric ﬁeld on the states of the hydrogen atom—the Stark eﬀect. It

is simplest to take the electric ﬁeld in the z direction, so that the perturbing

potential is −ecz. To take advantage of the symmetry of the perturbation,

consider the commutation properties of the potential with the operators such

as parity and angular momentum that deﬁne the basis states. In this case

the potential commutes with the z component of the angular momentum,

but not with the total angular momentum. This is signiﬁcant because since

V commutes with L

z

, it cannot change its eigenvalues. The matrix elements

of V between states with diﬀerent eigenvalues of L

z

are therefore zero. Fur-

thermore, V changes the parity of a state, and thus has no matrix elements

between states of the same parity. These facts allow us to see that many

of the matrix elements of V are zero without the necessity of calculating

them. Consider, for example, the simplest degenerate case, the n = 2 states

of hydrogen. There are four of them, [200`, [211`, [210`, and [21 −1`, where

the labels are the values of n, , and m. The only non-vanishing matrix

elements of V between all of these states are the ones between [210` and

[200`. All the others are zero because they have diﬀerent values of L

z

or

because they have the same parity or both. It is useful to order the states

so that the ones which are connected by V are adjacent. With the order

[211`, [210`, [200`, [21 −1`, the matrix takes the form

V =

¸

¸

¸

0 0 0 0

0 0 v

∗

0

0 v 0 0

0 0 0 0

¸

.

Only a single matrix element must be calculated, and its value is v =

'200[V [210`. It can be evaluated by using the explicit form of the state

from Chapter 7 but we will leave it as a symbol.

The matrix V is in what is known as block-diagonal form because of

the commutation and symmetry properties of V . The elements of a block-

diagonal matrix are zero except for square matrices of smaller dimension

that lie along the diagonal. Here the smaller matrices are 1 1, 2 2, and

1 1. The states corresponding to the 1 1 blocks are already eigenstates

of V . Although this in not generally the case, the matrix elements are zero

here because of the parity properties. All that remains is to ﬁnd the linear

superpositions of the two states corresponding to the 2 2 block that are

6

eigenstates of V , i.e., to diagonalize this block. This is easily done: the

eigenvalues are ±[v[ and the eigenstates are

1

2

[210` ±(v/[v[)

1

2

[200`. The

electric ﬁeld splits the fourfold degenerate n = 2 state of the hydrogen atom

into three levels, one of which is doubly degenerate and unshifted by the

ﬁeld. The two superpositions entail not only a shift of the energy by ±[v[,

but also a shift of the electric charge of the electron along the z axis, giving

the atom a dipole moment. A sketch of the wave functions is shown in

Fig.(1.1). The system thus acts as if it had a permanent dipole moment,

Figure 1.1: Wave function along the z axis of the lowest state in a hydrogen

atom perturbed by an electric ﬁeld (Stark Eﬀect). The dotted curves show

the 2s and 2p states that are superposed to obtain the state with a dipole

moment, shown as the solid curve.

and has an energy that is ﬁrst order in the ﬁeld. If the dipole moment is

along the ﬁeld, the energy is lower and if it is opposite the ﬁeld, the energy is

higher. The two states that are not shifted in energy cannot form dipoles by

superposition within the degenerate set, and their energy is therefore second

order in the ﬁeld. First order perturbation theory would mix states outside

the degenerate set to give the state an induced dipole moment proportional

to the ﬁeld. The second order energy would show the eﬀect of the ﬁeld on

this induced dipole. The atom in this state acts partly as a permanent dipole

and partly as an induced dipole, combining these two classical behaviors in

a single degenerate state of a single atom.

This example oﬀers a taste the remarkable rigidity of atoms that accounts

7

for the well-deﬁned geometry of atoms and molecules. Although a full dis-

cussion of this topic rests on the exclusion principle, we can see here that

deformation of electron orbits from the shape dictated by the Schr¨ odinger

equation, in this example by an electric ﬁeld, can sometimes be accomplished

only by superposing higher energy states. The consequent increase in energy

is the mechanism that provides rigidity. This case is exceptional in that two

of the states can be deformed to produce a dipole moment by superposing

a state of the same energy, constituting an unusual case where there is zero

rigidity.

1.3 The Zeeman Eﬀect in Hydrogen

The Hamiltonian that describes the interaction of a hydrogen atom with

an external magnetic ﬁeld is

H = H

0

+ V

SO

(r)

L

S + βBL

z

+ gβBS

z

. (1.15)

in which β is the electron magnetic moment factor e/2mc, and H

0

is the

hydrogen atom Hamiltonian without spin or external ﬁeld. The second term

on the right is the spin-orbit term discussed in the last chapter, and the last

two terms are the Zeeman terms, representing the interaction of the orbital

and spin magnetic moments with the external B ﬁeld. If the magnetic ﬁeld

is weak, the Zeeman terms are much smaller than the spin-orbit term, and

they can be treated as a perturbation while the spin-orbit term is taken as

part of the unperturbed Hamiltonian. In that case, the unperturbed states

are eigenstates of J

2

and J

z

as well as L

2

and S

2

, but not of L

z

and S

z

.

At the other extreme of strong B ﬁeld, the spin-orbit term is treated as a

perturbation and the unperturbed states are eigenstates of L

2

, S

2

, L

z

, and

S

z

. To avoid getting lost in generalities, let’s consider the case of the 2p

level in hydrogen. There are six of states, and their choice and labelling is

diﬀerent in the weak ﬁeld and strong ﬁeld cases.

(1.)Weak Field Case. The spin-orbit term splits the level into 2p3

2

and

2p1

2

states. The splitting can be found as described in Sec.(8.6). If v denotes

the expectation value of V

SO

(r) in the p state, then, according to Eq.(??),

the 2p3

2

level has energy v and the 2p1

2

level has energy −2v. Although

the perturbation does not commute with J

2

, it does commute with J

z

and

therefore cannot change J

z

. This means that it will be diagonal within each

unperturbed block of states, since each state in a multiplet has a diﬀerent

value of m

J

. To ﬁnd the energies it is only necessary to calculate the diagonal

elements of the perturbing terms with the aid of the speciﬁc formulas for the

8

eigenstates Eqs.(??) and (??). The resulting diagonal elements, which are

the Zeeman contrubution to the energy of the states, are ±2β and ±

2

3

β for

the 2p3

2

multiplet and ±

1

3

β for the 2p1

2

multiplet. The resulting spectrum

Figure 1.2: Weak ﬁeld Zeemann eﬀect. The 2p

1/2

state is two-fold degenerate

and the 2p

3/2

state is four-fold degenerate when only the spin-orbit term is

included. The magnetic ﬁeld splits the states (right) proportional to m

j

.

Figure 1.3: Strong ﬁeld Zeemann eﬀect. The states at the left omit the

spin-orbit coupling. The middle state is doubly degenerate. The perturbing

spin-orbit term removes the degeneracy and shifts the outer levels. The

second and fourth levels, corresponding to L

z

= 0 and S

z

= ±/2 are

unaﬀected.

9

is shown in Fig.(1.2)(a). It is a general feature of the weak ﬁeld Zeeman

splitting that the levels are equally spaced and proportional to m

J

.

(2.)Strong Field Case. The basis states are products of Y

1m

and either

[u` or [d`. These are eigenstates of the two Zeeman terms with eigenvalues

±2β, ±β, and zero. Only the zero eigenvalue is degenerate, the unper-

turbed states being Y

11

[d` and Y

1−1

[u`. The matrix elements of the perturb-

ing spin-orbit interaction can be calculated with the aid of the identity

L

S =

1

2

L

+

S

−

+

1

2

L

−

S

+

+ L

z

S

z

.

The ﬁrst two terms change the z components of the orbital and spin angular

momenta by one unit in opposite directions and the last term does not alter

them. From this we can see that there are no oﬀ-diagonal terms in the

degenerate block because the states in that block have orbital m values that

diﬀer by two units. Only the last term contributes to the diagonal elements,

and this term can be calculated directly. We conclude that the product

states remain the correct unperturbed states, and that the spectrum is as

shown in Fig. (1.3).

It would be fun to guess how the weak ﬁeld spectrum connects to the

strong ﬁeld spectrum. To answer the question rigorously, one could treat

all three terms as a perturbation. This would involve diagonalizing a 66

matix.

1.4 Time Dependent Perturbation Theory

Time dependent perturbation theory addresses the problem of ﬁnding the

transition rate from a given initial state to any ﬁnal state within a chosen

continuuum of states. Both the initial state and the ﬁnal state are assumed

to be eigenstates of an unperturbed Hamiltonian H

0

. In the abssence of

the perturbation V the initial state would be stationary and no transition

would occur. When the perturbation is turned on at t = 0, transitions to

the continuum begin. We will show that the total transition probability to

all states of the continuum is proportional to the time, i. e., that there is a

constant transition rate.

Let [0` denote the initial state with unperturbed energy E

0

, and [E` a

state of the contunuum with unperturbed energy E. Other variables might

be needed to specify the ﬁnal states, but we omit them for simplicity in

the exposition. The initial state could be either an isolated discrete state

or itself part of a continuum. At ﬁrst, we let the ﬁnal continuum states be

discrete but closely spaced, like the travelling wave states of a free particle in

10

a box. These are, in fact, the states in question in most of the applications

of time dependent perturbation theory. Later we will replace sums over

the continuum states by an integral including a density of states. Before

beginning we take the simplifying step of incorporating the diagonal matrix

element '0[V [0` into the energy E

0

, after which we can assume that '0[V [0`

is zero. If the wave function is written in the form

[ψ` = c

0

(t)e

−iE

0

t/

[0` +

¸

E

c

E

(t)e

−iEt

[E`, (1.16)

the coeﬃcients c

E

(t) are independent of time in the absence of V . Their time

variation is entirely due to the perturbation. This is evident when we sub-

stitute Eq.(1.16) into the Schr¨ odinger equation and solve for the derivatives

of the coeﬃcients:

i˙ c

0

=

¸

E

c

E

e

−i(E−E

0

)t

'0[V [E`,

i˙ c

E

= c

0

e

−i(E

0

−E)t/

'E[V [0` +

¸

E

c

E

e

−i(E

−E

0

)

t/'E[V [E

`.

These diﬀerential equations are to be solved subject to the initial conditions

c

0

(0) = 1 and c

E

(0) = 0 that indicate that the initial state is [0`. Note

that the coeﬃcient c

E

is at least ﬁrst order in V , since it vanishes in the

absence of the perturbation. The last terms in each diﬀerential equations

can now be seen to be of second order in V and can be omitted in ﬁrst order

perturbation theory. To this order, c

0

is a constant equal to unity, and the

second equation can be directly integrated to ﬁnd c

E

:

c

E

(t) =

1

i

t

0

e

−i(E

0

−E)t

/

'E[V [0`dt

=

1

i

e

−i(E

0

−E)t/

−1

−i(E

0

−E)/

'E[V [0`

= e

−

1

2

(E

0

−E)t/

−2i sin

1

2

(E

0

−E)t/

E

0

−E

'E[V [0`

The probability of ﬁnding the state [E` is

[c

E

(t)[

2

=

sin

2 1

2

(E

0

−E)t/

(

1

2

(E

0

−E))

2

['E[V [0`[

2

. (1.17)

This function is plotted in Fig(1.4). There is a peak at E = E

0

of height

proportional to t

2

, found by using the approximation sinx ≈ x when taking

11

the limit E → E

0

. The width of the peak can be measured from the ﬁrst

zeros to the right and left of the main peak, which occur at E = E

0

±

2π/t, giving a width proportional to 1/t. To evaluate the total transition

probability, we convert the sum over all the states in the continuum to an

integral by multiplying by the density of states ρ(E) and integrating over

E:

P =

[c

E

(t)[

2

ρ(E)dE.

To evaluate the integral, we note the following. The principal contribution

comes from the main peak. In fact, the probabilities for transitions to states

outside the main peak oscillate between zero and a ﬁnite value, so that there

are no permanent transitions to these states. The oscillations as well as the

transitions outside the main peak are actually artifacts of the sudden turning

on of the perturbation at t = 0. We will return to this point later. Since

the important transitions occur to states within a narrowing main peak,

it is a good approximation to evaluate both the density of states and the

matrix element at the center of the peak E = E

0

and factor them out of the

integral. The assumption here is that ρ(E) and 'E[V [0` are slowly varying

compared to the ﬁrst factor in Eq.(1.17) that deﬁnes the shape of the peak.

With these factors outside the integral sign, we are left with an integral that

can be evaluated by elementary means. The expected result is proportional

to t, since, as estimated above, the height or the peak is t

2

and the width

is 1/t. By explicit calculation, the result for the total transition probability

Figure 1.4: Plot of the function sin

2

(∆E/2)/(∆E/2)

2

12

to all states in the continuum is

[c

E

(t)[

2

ρ(E)dE =

2πt

['E[V [0`[

2

ρ(E), (1.18)

where the matrix element and the density of states are to be evaluated at

E = E

0

. This useful equation, the main result of time dependent perturba-

tion theory, is called Fermi’s Golden Rule.

It is possible to avoid the unphysical oscillations in the transition prob-

ability and the transitions to states outside the main peak by turning the

potential on slowly. This is done by replacing V by V e

t

and integrating

from −∞ to a ﬁnite time. The correct time is zero, because that is when

the potential reaches its actual value. The rate of change of [c

E

(t)[

2

at that

instant is then the transition rate due to the potential V . At the end of the

calculation, we can let go to zero. The details of this calculation will be

assigned as a problem. The result is the same as Eq.(1.18).

1.5 The Born Approximation

A frequent application of Fermi’s Golden Rule is to scattering problems.

The simplest of these is the scattering of a particle by a weak ﬁxed po-

tential V (r). The perturbation is the potential itself, and the unperturbed

Hamiltonian is the free particle Hamiltonian. The initial and ﬁnal states are

states of deﬁnite wave number

k

0

and

k. Since the scattering probability

may have considerable dependence on the angle of scattering, we cannot take

the entire continuum of free particle states as the ﬁnal state continuum in

the transition probability. Instead, it is necessary to take only those states

for which the propagation vector lies within an inﬁnitesimal solid angle dΩ

over which the matrix element can be assumed not to vary. In polar coor-

dinates, the element of solid angle is sin θdθdφ. This restricted set is still a

continuum because variation in the magnitude of

k will give a continuous

variation in the energy. Restricting consideration to a sub-continuum does

not imply that there are no transitions to states with propagation vectors

in other directions that take place simultanously with similar probabilities.

The matrix element for the transition is evaluated in the wave function

representation

'E[V [0` =

e

−i

k·r

√

1

V (r)

e

i

k

0

·r

√

1

d

3

r

By combining the exponentials, we see that the matrix element is the Fourier

transform of the potential evaluated at a wave number corresponding to the

13

momentum transfer (

k −

k

0

) to the scattered particle. The density of

states ρ(E) is deﬁned so that ρ(E)dE is the number of states in the energy

interval dE with propagation vectors in the solid angle dΩ centered about a

particular scattering direction.

Calculation of the density of states is slightly diﬀerent from the calcu-

lation in Chapter 2 because we are now dealing with travelling wave modes

instead of standing wave modes. The condition k

i

L = 2πn

i

must be satis-

ﬁed for each direction i = x, y, z, so the spacing between allowable values

of the components is 2π/L. The resulting density of states in k space is

1d

3

k/(2π)

3

. The volume element in k-space can be expressed in polar co-

ordinates as k

2

dkdΩ. The energy-momentum relation E =

2

k

2

/2m allows

us to translate the density of states into energy terms

ρ(E)dE =

m

√

2mE1

3

dE.

Substituting the matrix elements and density of states into the golden rule

Eq.(1.18) and dividing by the time, we ﬁnd the transition probability per

unit time into all states within the solid angle dΩ to be

w =

m

√

2mE

(2π)

2

1

4

e

i(

k−

k

0

·r

V (r)d

3

r

2

.

The transition probabilty is proportional to 1/1 because the initial state

has less and less probability density in the vicinity of the region where

the potential is important as the volume of quantization increases. We

are more interested in the probability that the particle is scattered given

that it approaches the target. The diﬀerential cross-section is a quantity

that measures this probability and which is at the same time amenable to

experimental measurement. It is deﬁned as

dσ

dΩ

=

# particles scattered per unit time per unit solid angle

# particles incident per unit time per unit area

(1.19)

The total cross-section σ is deﬁned as the integral of the diﬀerential cross-

section over all solid angle. It counts all particles scattered from the initial

beam. The dimensions of the cross-sections are (length)

2

. The diﬀerential

cross-section can be correctly thought of as the cross-sectional area of the

incident beam that gets scattered into dΩ. From an experimental point of

view, the deﬁntion of the diﬀerential cross-section tells us that the number

of particles scattered per unit time into solid angle dΩ by a single scatterer is

proportional to the magnitude of the solid angle and to the incident ﬂux j

in

14

(which is the denominator of the deﬁnition). The proportionality constant

is the diﬀerential cross-section: the rate is (dσ/dΩ)j

in

dΩ. When there are

many scatterers this has to be multiplied by the total number of scattering

centers ρA, where ρ is the density of centers in the material, A is the

cross-sectional area of the beam, and is the length of material traversed.

The numerator in Eq.(1.19) is the transition rate w calculated above, and

the denominator can be identiﬁed as the probability current of the initial

state. By direct calculation, this is k

0

/m1. Putting these together and

noting the the magnitudes of

k and

k

0

are equal gives us the diﬀerential

scattering cross-section to ﬁrst order in the scattering potential, the Born

approximation,

dσ

dΩ

=

m

2

4π

2

4

e

−i(

k−

k

0

)·r

V (r)d

3

r

2

(1.20)

As expected, this is independent of the quantization volume.

1.6 The Variational Method

The variational method is based on the fact that the smallest expectation

value the Hamiltonian can have is the ground state energy. If the expectation

value of H is taken with a wave function with parameters, the parameters

can be varied over their whole range and the expectation value will always

remain an upper bound for the ground state energy. A good upper limit

can be found by minimizing the expectation value with respect to the pa-

rameters. If you are good enough at guessing the form of the ground state

wave function, the upper bound will come close to the actual ground state

energy and your guess for both state and energy will be a good variational

approximation.

A formal proof that the expectation value of H in a generic state provides

an upper bound is obtained by expressing the expectation value in terms of

a complete set of energy eigenstates

'E` =

¸

E

E['E[ψ`[

2

.

If the E in the sum is replaced by the ground state energy E

0

, the expression

is certainly made smaller, i. e.,

'E` ≥ E

0

¸

E

['E[ψ`[

2

,

15

where E

0

has been factored out of the sum. The sum is unity because it

is the normalization condition for the state, expressing the total probability

that it is in one or other of the eigenstates of energy.

The variational method can be quite lengthy to apply because of the

labor of calculating the expectation value of the energy and the normalizing

constants. It is advisable to use some calculational aid such as Mathematica

to save calculational time. Here we will illustrate the method using the

harmonic oscillator, and show how reasonably good results can be obtained

even with a crude trial wave function. The trial wave function we use is an

inverted parabola:

ψ(x) =

0 for x < −

a/b

a −bx

2

for −

a/b < x <

a/b

0 for x >

a/b

Normalization of the wave function requires that b = 256a

5

/225, leaving

expectation values that depend on a single parameter a. In calculating the

expectation value of the kinetic energy, note that the ﬁrst derivative of the

wave function is discontinuous at x = ±

**a/b, causing the second derivative
**

to have a δ-function singularity there. In fact, the second derivative of the

wave function in the region where the wave function is non-vanishing is

ψ

= −2b + 2

√

abδ(x +

a/b) + 2

√

abδ(x −

a/b).

Calculation of the expectation value of the kinetic energy involves integrating

ψ

**ψ. The delta functions do not contribute because the wave function is
**

zero at the points where the singularities occur. Taking this behavior into

account, the expectation value of the energy is found to be

'E` =

64

45

2

m

a

4

+

225

3584

mω

2

a

4

,

where the ﬁrst term is the kinetic energy and the second is the potential en-

ergy. To ﬁnd the best upper bound for the ground state energy, we minimize

this expression with respect to a

4

to obtain

a

4

=

45

128

5

14

mω

.

Finally, the bound on the ground state energy is

E

0

≤ 'E` =

5

14

ω = 0.598ω,

16

about 20% above the actual ground state energy. Although the estimate is

not much better than a crude uncertainty principle estimate, we have the

satisfaction of knowing that it is deﬁnite an upper bound for the ground

state energy. The wave function bears only a vague resemblance to the

actual ground state wave function. The results would be better if we chose

a wave function closer to the actual one. For example, the wave function

cos kx is a little closer to the actual ground state wave function (a Gaussian)

because it spreads to the side a little more. If this were used, the bound

would be 0.568ω, a little better than the one above.

1.7 Problems

1. Find the energies of the lowest few states of an inﬁnite square well with

a small potential bump in the center. Let the bump have height V

0

much less than the ground state energy of the well, and width b much

smaller than the width of the well. Take the calculation to second

order, but do not attempt to sum any inﬁnite series that may arise.

2. Find the ﬁrst order correction to the energies of a harmonic oscillator

perturbed by the non-linear addition γx

4

to the potential (Although

the perturbation series is well deﬁned, it can be shown that it does

not converge in this problem).

3. The ﬁrst excited state of a particle in a 2-dimensional square box of

side a is degenerate. Find the energies of this state correct to ﬁrst

order in γ if it is perturbed by a potential

V (x, y) = γδ(x −

1

3

a)δ(y −

2

3

a),

where the origin is placed at the lower left corner of the box.

4. Show how the Stark Eﬀect splits the 3d state of hydrogen.

5. Find the correct unperturbed states and the spectrum to ﬁrst order in

the strong ﬁeld Zeeman eﬀect for the 3d state of hydrogen.

6. Show that the slowly turned on potential gives the same result for the

total transition probability as the calculation that preceeds Eq.(1.18).

7. Show that the harmonic potential

1

2

V

0

e

iωt

+

1

2

V

∗

0

e

−iωt

gives the same

result as a constant potential, except that there are two peaks at E

0

±

ω in the transition probability instead of a single peak at E

0

.

17

8. Apply the result of the previous problem to ﬁnd the probability that

an oscillating electric ﬁeld of frequency ω will ionize a hydrogen atom

in its ground state, sending its electron into a solid angle dΩ in some

direction. For the purposes of illustration only, (it is a poor approx-

imation quantitatively), take the ﬁnal state of the electron to be an

eigenstate of momentum.

9. Use the Born approximation to ﬁnd the diﬀerential cross section for

scattering a particle from a potential γδ(r − a

ˆ

i) + γδ(r + a

ˆ

i). Plot

the result as a function of the polar angle φ for θ = 0 for incident

wavelength a little less than the spacing 2a between the scatterers.

10. Find the best upper limit you can with a one parameter variational

method to the ground state of an electron in a potential

V =

∞ for x < 0

γx for x > 0

18

The ﬁrst order correction to the state is found by taking the inner product of Eq..5) + (2) n |ψn . The resulting equation can be solved for (1) φm |ψn : φm |V |φn (1) .. Superscripts in parentheses indicate the power of V to which the term is proportional.(1.7) The second term on the right of Eq. The ﬁrst term in the (1) (1) (1) left is φm |H0 |ψn = ψn |H0 |φm ∗ = m φm |ψn . If this is not true initially. As a result of this operation. (1. The state can be renormalized. The (1) (1) (1) ﬁrst term on the left is φn |H0 |ψn = ψn |H0 |φn ∗ = ψn | n |φn ∗ .(1. and the ﬁrst term on the right is zero by orthogonality. φm |ψn = n− m 2 .(1.6) and equations of higher order. the coeﬃcient of |φ n on the right of Eq. however. The ﬁrst order corrections to the energy and the state are determined by Eq. In Eq. ( En 1)|φn (2) En |φn (1.(1.7) says that the ﬁrst order correction to the energy is the expectation value of the perturbing potential in the unperturbed state.3) + (1) En (2) + En + . Eq.(1.4) (1) + n |ψn .2) (1. the corrections to the state can be expanded in terms of the unperturbed eigenstates.. which vanishes for the same reason. and the terms involving |φn can moved to the left and combined with the |φ n term in the expansion.5) makes no contribution because of the orthogonality of the higher corrections to the unperturbed state. the order of the term. Take its inner product with φ n | to get (1) φn |V |φn = En (1. n (1.2) it can be assumed without (p) loss of generality that the higher order corrections |ψ n are orthogonal to the unperturbed state |φn .multiplicatively): |ψn En = (1) (2) = |φn + |ψn + |ψn + .3) are substituted into the eigenvalue equation H|ψ n = En |ψn and the terms of same order equated.2) is no longer unity.5 with φ m | with m = n.2) and (1. we obtain H0 |φn (1) H0 |ψn + V |φn (2) (1) H0 |ψn + V |ψn = = = n |φn .(1.(1.5). The remaining terms are all orthogonal to |φ n . The ﬁrst equation is of zero order in V and aﬃrms that the unperturbed state is an eigenstate of the unperturbed Hamiltonian. by dividing by this coeﬃcient leaving an expansion of the given form with all corrections orthogonal to the unperturbed state. (1) (1) + En |ψn (1.. If Eqs.

we consider a charged harmonic oscillator perturbed by an electric ﬁeld. and proceed now assuming no degeneracy.(1. Here we will go only to ﬁrst order in the state and second order in the energy where the results are simple enough to be useful.8) n− m m=n m=n If one or more of the states |φm is degenerate with the unperturbed state. The perturbing potential is √ V = −eEx = −(eE / 2)(a† + a).from which the expansion of the ﬁrst order correction can be constructed as φm |V |φn (1) (1) |ψn = |φm φm |ψn = |φm (1. Using Eq. We will return to this problem of degenerate perturbations later.6) above yields φ n |V |ψn = En . The unperturbed Hamiltonian is H0 = (a† a+1 ) ω. the denominator in the last equation vanishes and Eq. we let V act on an unperturbed state: √ eE √ V |n = − √ n + 1 |n + 1 + n |n − 1 . its eigenvalues are (n+1 ) ω.8) we ﬁnd (2) En = m = m | φn |V |φm |2 n− m φn |V |φm φm |V |φn n− m (1.9) As an example of the application of non-degenerate perturbation theory. Perturbation theory can be carried to any order in principle.(1. 2 From this equation we obtain the ﬁrst and second order corrections to the energy: (1) En = = 0 (2) En = n|V |n | m|V |n |2 n− m + 1) − ω + 1 e2 E 2 2 n 2 = m=n 1 e2 E 2 2 (n 2 ω = − e2 E 2 2 2 ω 3 .8) becomes meaningless. The inner product of φ n | with the second (1) (2) order equation (1. 2 2 and its eigenstates will be denoted by |n . but it becomes more and more involved as the order increases. To construct the matrix elements of V that enter the perturbation formulas. Contributions from the ﬁrst term on the left and the second and third terms on the right are zero by the same arguments as before.

so that the charge distribution is no longer centered at the origin.9) come only from states which are not degenerate with the unperturbed state. A set of n degenerate eigenstates is not unique because any orthonormal set of n independent linear combinations of the original set is also a set of degenerate states with the same energy eigenvalue. because the full Hamiltonian is exactly soluble. like the eﬀect of gravity on a hanging spring. which in this case takes the form |ψn = |n − 1 2 2 2 (n 2e E + 1) ω |n + 1 + 1 e2 E 2 2 n 2 ω |n − 1 . The eigenstate |ψn correct to ﬁrst 2 order is given by Eq. Here because of the special properties of the harmonic oscillator.8). this example is only intended to illustrate the workings of perturbation theory. The oﬀ-diagonal elements can be made to vanish by choosing the eigenstates of V within the degenerate set as a new set of unperturbed states. The perturbed system is still an oscillator of frequency ω. The energy shift represents the interaction of the induced dipole moment with the ﬁeld.(1. is to shift the equilibrium point and the equilibrium energy without aﬀecting the frequency of oscillation.(1. The physical interpretation of the added corrections can be seen by reexpressing this equation in wave function form and plotting the resulting wave patterns. The physical reason for this is that the eﬀect of the electric ﬁeld.9).(1. With the oﬀdiagonal elements eliminated.(1.8) and (1. In fact. the ﬁrst order corrections to the state Eq.Thus the second order perturbation theory result for the energy of the n-th state is En = (n+1 ) ω − (e2 E 2 2 /2 ω).8) and the second order corrections to the energy Eq. We can use this freedom of choice to eliminate the oﬀ-diagonal elements of the matrix representing V within the degenerate set and thereby eliminate the oﬀending terms in Eqs. the sum involved in the second order eigenvalue and the ﬁrst order eigenstate contain only two terms. so that the energy levels remain equally spaced. It is quadratic in the ﬁeld because the induced moment is proportional to the ﬁeld and the energy is the product of the ﬁeld with the moment. The singular denominators that cause diﬃculties in the degenerate case can be avoided by choosing the basis states properly. Normally the series would be inﬁnite. Another special harmonic oscillator feature is that the energy correction is a constant independent of the unperturbed state. The eﬀect is to shift the wave function slightly in the direction of the electric force. Thus the electric ﬁeld induces an electrice dipole moment with respect to the origin. and would have to be evaluated numerically. This and other examples of the application of perturbation theory to non-degenerate states are left to the problems. No vanishing 4 .

Consider the eﬀect of the perturbation on the second excited state.14) .12). Detailed calculation of these corrections is omitted. Eq. 5 These are the ﬁrst order energies and the new unperturbed eignestates.10)-(1. which comprises the threefold degenerate set |20 . and |02 . and |00 that appear on the right side of Eqs. √ √ 3|13 + 2|11 √ √ 2|20 + 2|02 + |00 and −γ 2 and the corresponding normalized 1 2 1 2 1 2 |φ1 = with no oﬀ-diagonal elements. (1. 1 2 |φ2 = 1 2 1 2 1 2 .(1. |13 .10) (1. The action of V on each of the basis states is easily calculated by expressing V in terms of the raising and lowering operators as γ( 2 /2)(a† +ax )(a† +ay ): x y V |20 V |11 V |02 = = = γ 2 γ 2 γ 2 2 2 √ √ 3|31 + 2|11 2|22 + .7) then tells us that the ﬁrst order corrections to the energy are the diagonal elements of V in the new basis. These correction to the energy and state involve ﬁnite sums. Denote the eigenstates by |nx ny . we need the matrix representing V within the degenerate set: 0 1 0 2 γ (1. Matrix elements of V that would add other states are zero. the matrix representing V takes the form 0 0 0 0 V =γ 2 0 1 0 0 −1 − 0 . Using the new states as a basis. |11 . (1.13) V = √ 1 0 1 2 0 1 0 The eigenvalues are 0. To ﬁnd the ﬁrst order energy corrections. (1. γ eigenstates are 1 2 2. The procedure is best explained by an example.denominators occur. (1. The unperturbed eigenvalues (nx + ny + 1) ω are degenerate.11) . |22 . Consider an isotropic harmonic oscillator in two dimensions perturbed by a potential V = γxy. |φ3 = − . . First order corrections to the state and second order corrections to the energy will involve only the states |31 .12) 2 The operator V results in states both inside and outside the degenerate set.

the matrix elements are zero here because of the parity properties.1. It is simplest to take the electric ﬁeld in the z direction. To take advantage of the symmetry of the perturbation. 0 0 0 0 Only a single matrix element must be calculated. |210 . 2 × 2. the simplest degenerate case. With the order |211 . |200 . Although this in not generally the case. All the others are zero because they have diﬀerent values of L z or because they have the same parity or both. Furthermore. |211 . V changes the parity of a state. consider the commutation properties of the potential with the operators such as parity and angular momentum that deﬁne the basis states. It is useful to order the states so that the ones which are connected by V are adjacent.2 The Stark Eﬀect in Hydrogen The importance of symmetry in the application of perturbation theory to problems involving degeneracy is illustrated in the calculation of the eﬀect of an electric ﬁeld on the states of the hydrogen atom—the Stark eﬀect. The matrix V is in what is known as block-diagonal form because of the commutation and symmetry properties of V . and 1 × 1. . The only non-vanishing matrix elements of V between all of these states are the ones between |210 and |200 . |200 . but not with the total angular momentum. The elements of a blockdiagonal matrix are zero except for square matrices of smaller dimension that lie along the diagonal. so that the perturbing potential is −eEz. The matrix elements of V between states with diﬀerent eigenvalues of L z are therefore zero. The states corresponding to the 1 × 1 blocks are already eigenstates of V . the matrix takes the form 0 0 0 0 0 0 v∗ 0 V = 0 v 0 0 . It can be evaluated by using the explicit form of the state from Chapter 7 but we will leave it as a symbol. |210 . for example. There are four of them. and m. These facts allow us to see that many of the matrix elements of V are zero without the necessity of calculating them. the n = 2 states of hydrogen. and thus has no matrix elements between states of the same parity. it cannot change its eigenvalues. Consider. |21 − 1 . Here the smaller matrices are 1 × 1. and |21 − 1 . and its value is v = 200|V |210 . where the labels are the values of n. All that remains is to ﬁnd the linear superpositions of the two states corresponding to the 2 × 2 block that are 6 . In this case the potential commutes with the z component of the angular momentum. This is signiﬁcant because since V commutes with Lz .

The dotted curves show the 2s and 2p states that are superposed to obtain the state with a dipole moment.1: Wave function along the z axis of the lowest state in a hydrogen atom perturbed by an electric ﬁeld (Stark Eﬀect).eigenstates of V .1). and their energy is therefore second order in the ﬁeld. The 2 2 electric ﬁeld splits the fourfold degenerate n = 2 state of the hydrogen atom into three levels. First order perturbation theory would mix states outside the degenerate set to give the state an induced dipole moment proportional to the ﬁeld. giving the atom a dipole moment. This example oﬀers a taste the remarkable rigidity of atoms that accounts 7 . The two superpositions entail not only a shift of the energy by ±|v|. but also a shift of the electric charge of the electron along the z axis. This is easily done: the eigenvalues are ±|v| and the eigenstates are 1 |210 ± (v/|v|) 1 |200 . to diagonalize this block. i. one of which is doubly degenerate and unshifted by the ﬁeld. shown as the solid curve. Figure 1. combining these two classical behaviors in a single degenerate state of a single atom. The system thus acts as if it had a permanent dipole moment.. The two states that are not shifted in energy cannot form dipoles by superposition within the degenerate set.e. The second order energy would show the eﬀect of the ﬁeld on this induced dipole. The atom in this state acts partly as a permanent dipole and partly as an induced dipole. and has an energy that is ﬁrst order in the ﬁeld. the energy is lower and if it is opposite the ﬁeld.(1. If the dipole moment is along the ﬁeld. the energy is higher. A sketch of the wave functions is shown in Fig.

(1. representing the interaction of the orbital and spin magnetic moments with the external B ﬁeld. the spin-orbit term is treated as a perturbation and the unperturbed states are eigenstates of L 2 . and their choice and labelling is diﬀerent in the weak ﬁeld and strong ﬁeld cases. Although a full discussion of this topic rests on the exclusion principle. the Zeeman terms are much smaller than the spin-orbit term. S 2 . we can see here that deformation of electron orbits from the shape dictated by the Schr¨dinger o equation.(??).6). can sometimes be accomplished only by superposing higher energy states.(8.3 The Zeeman Eﬀect in Hydrogen The Hamiltonian that describes the interaction of a hydrogen atom with an external magnetic ﬁeld is H = H0 + VSO (r)L · S + βBLz + gβBSz . To ﬁnd the energies it is only necessary to calculate the diagonal elements of the perturbing terms with the aid of the speciﬁc formulas for the 8 . but not of Lz and Sz . and Sz . according to Eq. the unperturbed states are eigenstates of J 2 and Jz as well as L2 and S 2 . This means that it will be diagonal within each unperturbed block of states. In that case. the 2p3 level has energy v and the 2p1 level has energy −2v. This case is exceptional in that two of the states can be deformed to produce a dipole moment by superposing a state of the same energy. If the magnetic ﬁeld is weak. There are six of states. The spin-orbit term splits the level into 2p 3 and 2 2p1 states. constituting an unusual case where there is zero rigidity. (1. To avoid getting lost in generalities. and H 0 is the hydrogen atom Hamiltonian without spin or external ﬁeld. then. it does commute with Jz and therefore cannot change Jz .for the well-deﬁned geometry of atoms and molecules. 1. and they can be treated as a perturbation while the spin-orbit term is taken as part of the unperturbed Hamiltonian. let’s consider the case of the 2p level in hydrogen. At the other extreme of strong B ﬁeld. and the last two terms are the Zeeman terms. since each state in a multiplet has a diﬀerent value of mJ . If v denotes 2 the expectation value of VSO (r) in the p state. Lz .)Weak Field Case. The splitting can be found as described in Sec. Although 2 2 the perturbation does not commute with J 2 . The second term on the right is the spin-orbit term discussed in the last chapter. The consequent increase in energy is the mechanism that provides rigidity. in this example by an electric ﬁeld.15) in which β is the electron magnetic moment factor e/2mc.

are ±2β and ± 2 β for 3 the 2p2 multiplet and ±1 β for the 2p1 multiplet. The resulting spectrum 3 3 2 Figure 1.2: Weak ﬁeld Zeemann eﬀect. The perturbing spin-orbit term removes the degeneracy and shifts the outer levels.3: Strong ﬁeld Zeemann eﬀect. The middle state is doubly degenerate. The second and fourth levels. 9 .eigenstates Eqs.(??) and (??). which are the Zeeman contrubution to the energy of the states. Figure 1. The resulting diagonal elements. The 2p 1/2 state is two-fold degenerate and the 2p3/2 state is four-fold degenerate when only the spin-orbit term is included. The magnetic ﬁeld splits the states (right) proportional to m j . corresponding to L z = 0 and Sz = ± /2 are unaﬀected. The states at the left omit the spin-orbit coupling.

When the perturbation is turned on at t = 0. At ﬁrst. i. It is a general feature of the weak ﬁeld Zeeman splitting that the levels are equally spaced and proportional to m J . but we omit them for simplicity in the exposition.3). Let |0 denote the initial state with unperturbed energy E 0 . that there is a constant transition rate. transitions to the continuum begin. The initial state could be either an isolated discrete state or itself part of a continuum. These are eigenstates of the two Zeeman terms with eigenvalues ±2β . (1.2)(a). the unperturbed states being Y11 |d and Y1−1 |u . We conclude that the product states remain the correct unperturbed states.)Strong Field Case. To answer the question rigorously. ±β . Other variables might be needed to specify the ﬁnal states. From this we can see that there are no oﬀ-diagonal terms in the degenerate block because the states in that block have orbital m values that diﬀer by two units. Only the last term contributes to the diagonal elements.. It would be fun to guess how the weak ﬁeld spectrum connects to the strong ﬁeld spectrum. and that the spectrum is as shown in Fig. like the travelling wave states of a free particle in 10 . and |E a state of the contunuum with unperturbed energy E. We will show that the total transition probability to all states of the continuum is proportional to the time. and zero.is shown in Fig. one could treat all three terms as a perturbation. This would involve diagonalizing a 6×6 matix. and this term can be calculated directly. In the abssence of the perturbation V the initial state would be stationary and no transition would occur. 1. e.(1. 2 2 The ﬁrst two terms change the z components of the orbital and spin angular momenta by one unit in opposite directions and the last term does not alter them. The basis states are products of Y 1m and either |u or |d . Only the zero eigenvalue is degenerate. Both the initial state and the ﬁnal state are assumed to be eigenstates of an unperturbed Hamiltonian H 0 .4 Time Dependent Perturbation Theory Time dependent perturbation theory addresses the problem of ﬁnding the transition rate from a given initial state to any ﬁnal state within a chosen continuuum of states. The matrix elements of the perturbing spin-orbit interaction can be calculated with the aid of the identity L · S = 1 L+ S− +1 L− S+ + L z Sz . we let the ﬁnal continuum states be discrete but closely spaced. (2.

since it vanishes in the absence of the perturbation. (1. This is evident when we substitute Eq. c 0 is a constant equal to unity. These diﬀerential equations are to be solved subject to the initial conditions c0 (0) = 1 and cE (0) = 0 that indicate that the initial state is |0 . found by using the approximation sin x ≈ x when taking 11 . To this order. These are. and the second equation can be directly integrated to ﬁnd c E : cE (t) = 1 t −i(E0 −E)t / e E|V |0 dt i 0 1 e−i(E0 −E)t/ − 1 = E|V |0 i −i(E0 − E)/ −2i sin 1 (E0 − E)t/ 1 2 = e−2 (E0 −E)t/ E0 − E E|V |0 The probability of ﬁnding the state |E is |cE (t)|2 = sin2 1 (E0 − E)t/ 2 | E|V |0 |2 .(1. (1 (E0 − E))2 2 (1. after which we can assume that 0|V |0 is zero.16) into the Schr¨dinger equation and solve for the derivatives o of the coeﬃcients: i c0 = ˙ E cE e−i(E−E0 )t 0|V |E . the states in question in most of the applications of time dependent perturbation theory. in fact. Before beginning we take the simplifying step of incorporating the diagonal matrix element 0|V |0 into the energy E0 . Their time variation is entirely due to the perturbation. Later we will replace sums over the continuum states by an integral including a density of states.17) This function is plotted in Fig(1. There is a peak at E = E 0 of height proportional to t2 .a box. Note that the coeﬃcient cE is at least ﬁrst order in V . E i cE ˙ = c0 e−i(E0 −E)t/ E|V |0 + cE e−i(E −E0 ) t/ E|V |E . The last terms in each diﬀerential equations can now be seen to be of second order in V and can be omitted in ﬁrst order perturbation theory.4).16) E the coeﬃcients cE (t) are independent of time in the absence of V . If the wave function is written in the form |ψ = c0 (t)e−iE0 t/ |0 + cE (t)e−iEt |E .

we note the following. Since the important transitions occur to states within a narrowing main peak.4: Plot of the function sin 2 (∆E/2 )/(∆E/2)2 12 . so that there are no permanent transitions to these states. We will return to this point later. we are left with an integral that can be evaluated by elementary means. The width of the peak can be measured from the ﬁrst zeros to the right and left of the main peak. By explicit calculation. giving a width proportional to 1/t. we convert the sum over all the states in the continuum to an integral by multiplying by the density of states ρ(E) and integrating over E: P = |cE (t)|2 ρ(E)dE. the height or the peak is t 2 and the width is 1/t.17) that deﬁnes the shape of the peak. To evaluate the integral. With these factors outside the integral sign. the result for the total transition probability Figure 1. In fact.(1. which occur at E = E 0 ± 2π /t.the limit E → E0 . as estimated above. the probabilities for transitions to states outside the main peak oscillate between zero and a ﬁnite value. The expected result is proportional to t. The assumption here is that ρ(E) and E|V |0 are slowly varying compared to the ﬁrst factor in Eq. since. The oscillations as well as the transitions outside the main peak are actually artifacts of the sudden turning on of the perturbation at t = 0. To evaluate the total transition probability. The principal contribution comes from the main peak. it is a good approximation to evaluate both the density of states and the matrix element at the center of the peak E = E 0 and factor them out of the integral.

Restricting consideration to a sub-continuum does not imply that there are no transitions to states with propagation vectors in other directions that take place simultanously with similar probabilities. The details of this calculation will be assigned as a problem. In polar coordinates. At the end of the calculation. Instead. 1.to all states in the continuum is |cE (t)|2 ρ(E)dE = 2πt | E|V |0 |2 ρ(E). the main result of time dependent perturbation theory. is called Fermi’s Golden Rule. It is possible to avoid the unphysical oscillations in the transition probability and the transitions to states outside the main peak by turning the potential on slowly. The perturbation is the potential itself. The simplest of these is the scattering of a particle by a weak ﬁxed potential V (r). the element of solid angle is sin θdθdφ. (1. it is necessary to take only those states for which the propagation vector lies within an inﬁnitesimal solid angle dΩ over which the matrix element can be assumed not to vary. and the unperturbed Hamiltonian is the free particle Hamiltonian. Since the scattering probability may have considerable dependence on the angle of scattering.18). This useful equation. The matrix element for the transition is evaluated in the wave function representation eik0 ·r e−ik·r √ V (r) √ d3 r E|V |0 = V V By combining the exponentials. The initial and ﬁnal states are states of deﬁnite wave number k0 and k. we cannot take the entire continuum of free particle states as the ﬁnal state continuum in the transition probability. we see that the matrix element is the Fourier transform of the potential evaluated at a wave number corresponding to the 13 . because that is when the potential reaches its actual value. This restricted set is still a continuum because variation in the magnitude of k will give a continuous variation in the energy. The result is the same as Eq. This is done by replacing V by V e t and integrating from −∞ to a ﬁnite time. The correct time is zero.(1.18) where the matrix element and the density of states are to be evaluated at E = E0 . The rate of change of |c E (t)|2 at that instant is then the transition rate due to the potential V . we can let go to zero.5 The Born Approximation A frequent application of Fermi’s Golden Rule is to scattering problems.

19) The total cross-section σ is deﬁned as the integral of the diﬀerential crosssection over all solid angle. The volume element in k-space can be expressed in polar coordinates as k 2 dkdΩ. the deﬁntion of the diﬀerential cross-section tells us that the number of particles scattered per unit time into solid angle dΩ by a single scatterer is proportional to the magnitude of the solid angle and to the incident ﬂux j in 14 . so the spacing between allowable values of the components is 2π/L.18) and dividing by the time. we ﬁnd the transition probability per unit time into all states within the solid angle dΩ to be √ 2 m 2mE ei(k−k0 ·r V (r)d3 r .(1. We are more interested in the probability that the particle is scattered given that it approaches the target. The energy-momentum relation E = 2 k 2 /2m allows us to translate the density of states into energy terms √ m 2mEV ρ(E)dE = dE. The condition k i L = 2πni must be satisﬁed for each direction i = x. The diﬀerential cross-section can be correctly thought of as the cross-sectional area of the incident beam that gets scattered into dΩ. Calculation of the density of states is slightly diﬀerent from the calculation in Chapter 2 because we are now dealing with travelling wave modes instead of standing wave modes. From an experimental point of view. The diﬀerential cross-section is a quantity that measures this probability and which is at the same time amenable to experimental measurement. y. w= (2π)2 V 4 The transition probabilty is proportional to 1/V because the initial state has less and less probability density in the vicinity of the region where the potential is important as the volume of quantization increases. It counts all particles scattered from the initial beam. The resulting density of states in k space is Vd3 k/(2π)3 . The density of states ρ(E) is deﬁned so that ρ(E)dE is the number of states in the energy interval dE with propagation vectors in the solid angle dΩ centered about a particular scattering direction.momentum transfer (k − k0 ) to the scattered particle. 3 Substituting the matrix elements and density of states into the golden rule Eq. z. It is deﬁned as dσ # particles scattered per unit time per unit solid angle = dΩ # particles incident per unit time per unit area (1. The dimensions of the cross-sections are (length) 2 .

. The proportionality constant is the diﬀerential cross-section: the rate is (dσ/dΩ)j in dΩ.(1.19) is the transition rate w calculated above. If the E in the sum is replaced by the ground state energy E 0 . m2 dσ = 2 4 dΩ 4π 2 e−i(k−k0 )·r V (r)d3 r (1. E ≥ E0 | E|ψ |2 . this is k 0 /mV. where ρ is the density of centers in the material. A good upper limit can be found by minimizing the expectation value with respect to the parameters. If the expectation value of H is taken with a wave function with parameters.20) As expected. A formal proof that the expectation value of H in a generic state provides an upper bound is obtained by expressing the expectation value in terms of a complete set of energy eigenstates E = E E| E|ψ |2 . E 15 . and is the length of material traversed. the expression is certainly made smaller. i. this is independent of the quantization volume. the Born approximation.6 The Variational Method The variational method is based on the fact that the smallest expectation value the Hamiltonian can have is the ground state energy. When there are many scatterers this has to be multiplied by the total number of scattering centers ρA . 1.(which is the denominator of the deﬁnition). and the denominator can be identiﬁed as the probability current of the initial state. Putting these together and noting the the magnitudes of k and k0 are equal gives us the diﬀerential scattering cross-section to ﬁrst order in the scattering potential. the upper bound will come close to the actual ground state energy and your guess for both state and energy will be a good variational approximation. the parameters can be varied over their whole range and the expectation value will always remain an upper bound for the ground state energy. If you are good enough at guessing the form of the ground state wave function. By direct calculation. The numerator in Eq. A is the cross-sectional area of the beam. e.

14 16 . 14 Finally. the bound on the ground state energy is E0 ≤ E = 5 ω = 0. Here we will illustrate the method using the harmonic oscillator. The variational method can be quite lengthy to apply because of the labor of calculating the expectation value of the energy and the normalizing constants. causing the second derivative to have a δ-function singularity there. we minimize this expression with respect to a4 to obtain a4 = 45 128 5 mω .where E0 has been factored out of the sum. The sum is unity because it is the normalization condition for the state. and show how reasonably good results can be obtained even with a crude trial wave function. Calculation of the expectation value of the kinetic energy involves integrating ψ ψ. leaving expectation values that depend on a single parameter a. The delta functions do not contribute because the wave function is zero at the points where the singularities occur. expressing the total probability that it is in one or other of the eigenstates of energy. Taking this behavior into account. To ﬁnd the best upper bound for the ground state energy. In calculating the expectation value of the kinetic energy.598 ω. In fact. It is advisable to use some calculational aid such as Mathematica to save calculational time. The trial wave function we use is an inverted parabola: 0 for x < − a/b 2 for − a/b < x < ψ(x) = a − bx a/b 0 for x > a/b Normalization of the wave function requires that b = 256a 5 /225. note that the ﬁrst derivative of the wave function is discontinuous at x = ± a/b. the expectation value of the energy is found to be E = 225 mω 2 64 2 4 . the second derivative of the wave function in the region where the wave function is non-vanishing is √ √ ψ = −2b + 2 abδ(x + a/b) + 2 abδ(x − a/b). a + 45 m 3584 a4 where the ﬁrst term is the kinetic energy and the second is the potential energy.

but do not attempt to sum any inﬁnite series that may arise.18). the wave function cos kx is a little closer to the actual ground state wave function (a Gaussian) because it spreads to the side a little more. 2. Show that the harmonic potential 1 V0 eiωt +1 V0∗ e−iωt gives the same 2 2 result as a constant potential. except that there are two peaks at E 0 ± ω in the transition probability instead of a single peak at E 0 . 1. Show how the Stark Eﬀect splits the 3d state of hydrogen. The ﬁrst excited state of a particle in a 2-dimensional square box of side a is degenerate. The wave function bears only a vague resemblance to the actual ground state wave function. and width b much smaller than the width of the well. 4. we have the satisfaction of knowing that it is deﬁnite an upper bound for the ground state energy. The results would be better if we chose a wave function closer to the actual one. 3 3 where the origin is placed at the lower left corner of the box. 17 . it can be shown that it does not converge in this problem). Take the calculation to second order. Find the energies of this state correct to ﬁrst order in γ if it is perturbed by a potential V (x. Find the energies of the lowest few states of an inﬁnite square well with a small potential bump in the center. For example. Let the bump have height V 0 much less than the ground state energy of the well.7 Problems 1. 3. 6. 7. the bound would be 0.(1. If this were used. a little better than the one above.about 20% above the actual ground state energy. Find the ﬁrst order correction to the energies of a harmonic oscillator perturbed by the non-linear addition γx 4 to the potential (Although the perturbation series is well deﬁned. Find the correct unperturbed states and the spectrum to ﬁrst order in the strong ﬁeld Zeeman eﬀect for the 3d state of hydrogen.568 ω. y) = γδ(x −1 a)δ(y −2 a). 5. Show that the slowly turned on potential gives the same result for the total transition probability as the calculation that preceeds Eq. Although the estimate is not much better than a crude uncertainty principle estimate.

For the purposes of illustration only. Use the Born approximation to ﬁnd the diﬀerential cross section for scattering a particle from a potential γδ(r − aˆ + γδ(r + aˆ Plot i) i).8. (it is a poor approximation quantitatively). Find the best upper limit you can with a one parameter variational method to the ground state of an electron in a potential V = ∞ for x < 0 γx for x > 0 18 . the result as a function of the polar angle φ for θ = 0 for incident wavelength a little less than the spacing 2a between the scatterers. take the ﬁnal state of the electron to be an eigenstate of momentum. sending its electron into a solid angle dΩ in some direction. Apply the result of the previous problem to ﬁnd the probability that an oscillating electric ﬁeld of frequency ω will ionize a hydrogen atom in its ground state. 10. 9.

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