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- 1 INTRODUCTION
- 1 Introduction
- 1.1 Major sources
- 2 FUNDAMENTAL CONCEPTS
- 2 Fundamental concepts
- 2.1 The breakdown of classical physics
- 2.2 The polarization of photons
- 2.3 The fundamental principles of quantum mechanics 2 FUNDAMENTAL CONCEPTS
- 2.3 The fundamental principles of quantum mechanics
- 2.4 Ket space
- 2.5 Bra space
- 2.6 Operators
- 2.7 The outer product
- 2.8 Eigenvalues and eigenvectors
- 2.9 Observables
- 2.10 Measurements
- 2.11 Expectation values
- 2.12 Degeneracy
- 2.13 Compatible observables
- 2.14 The uncertainty relation
- 2.15 Continuous spectra
- 3 POSITION AND MOMENTUM
- 3 Position and momentum
- 3.1 Introduction
- 3.2 Poisson brackets
- 3.3 Wave-functions
- 3.4 Schr¨odinger’s representation - I
- 3.5 Schr¨odinger’s representation - II
- 3.6 The momentum representation
- 3.7 The uncertainty relation
- 3.8 Displacement operators
- 4 QUANTUM DYNAMICS
- 4 Quantum dynamics
- 4.1 Schr¨odinger’s equations of motion
- 4.2 Heisenberg’s equations of motion
- 4.3 Ehrenfest’s theorem
- 4.4 Schr¨odinger’s wave-equation
- 5 ANGULAR MOMENTUM
- 5 Angular momentum
- 5.1 Orbital angular momentum
- 5.2 Eigenvalues of angular momentum
- 5.3 Rotation operators
- 5.4 Eigenfunctions of orbital angular momentum
- 5.5 Motion in a central ﬁeld
- 5.6 Energy levels of the hydrogen atom
- 5.7 Spin angular momentum
- 5.8 Wave-function of a spin one-half particle
- 5.9 Rotation operators in spin space
- 5.10 Magnetic moments
- 5.11 Spin precession
- 5.12 Pauli two-component formalism
- 5.13 Spin greater than one-half systems
- 5.14 Addition of angular momentum
- 6 APPROXIMATION METHODS
- 6 Approximation methods
- 6.1 Introduction
- 6.2 The two-state system
- 6.3 Non-degenerate perturbation theory
- 6.4 The quadratic Stark effect
- 6.5 Degenerate perturbation theory
- 6.6 The linear Stark effect
- 6.7 Fine structure
- 6.8 The Zeeman effect
- 6.9 Time-dependent perturbation theory
- 6.10 The two-state system
- 6.11 Spin magnetic resonance
- 6.12 The Dyson series
- 6.13 Constant perturbations
- 6.14 Harmonic perturbations
- 6.15 Absorption and stimulated emission of radiation
- 6.16 The electric dipole approximation
- 6.17 Energy-shifts and decay-widths
- 7 SCATTERING THEORY
- 7 Scattering theory
- 7.1 Introduction
- 7.2 The Lipmann-Schwinger equation
- 7.3 The Born approximation
- 7.4 Partial waves
- 7.5 The optical theorem
- 7.6 Determination of phase-shifts
- 7.7 Hard sphere scattering
- 7.8 Low energy scattering
- 7.9 Resonances

Consider a constant perturbation which is suddenly switched on at time t = 0:

H1(t) = 0

for t < 0

H1(t) = H1

for t≥0,

(6.206)

where H1 is time-independent, but is generally a function of the position, mo-

mentum, and spin operators. Suppose that the system is deﬁnitely in state |i at

time t = 0. According to Eqs. (6.200)–(6.202) (with t0 = 0),

c(0)

n (t) = δin,

(6.207)

c(1)

n (t) = − i

¯h Hni

t

0

exp[iωni (t −t)]dt

= Hni

En −Ei

[1− exp(iωnit)],

(6.208)

giving

Pi→n(t) |c(1)

n |2

= 4|Hni|2

|En −Ei|2 sin2

(En −Ei)t

2¯h

,

(6.209)

for i = n. The transition probability between states |i and |n can be written

Pi→n(t) = |Hni|2

t2

¯h2 sinc2

(En −Ei)t

2¯h

,

(6.210)

where

sinc(x) = sinx

x .

(6.211)

The sinc function is highly oscillatory, and decays like 1/|x| at large |x|. It is a

good approximation to say that sinc(x) is small except when |x|* <
*

∼ π. It follows

that the transition probability, Pi→n, is small except when

|En −Ei|* <
*

∼

2π¯h

t .

(6.212)

Note that in the limit t→∞only those transitions which conserve energy (i.e.,

En = Ei) have an appreciable probability of occurrence. At ﬁnite t, is is possible

to have transitions which do not exactly conserve energy, provided that

∆E∆t* <
*

∼ ¯h,

(6.213)

154

6.13 Constant perturbations

6 APPROXIMATION METHODS

where ∆E = |En − Ei| is change in energy of the system associated with the

transition, and ∆t = t is the time elapsed since the perturbation was switched

on. Clearly, this result is just a manifestation of the well-known uncertainty re-

lation for energy and time. This uncertainty relation is fundamentally different

to the position-momentum uncertainty relation, since in non-relativistic quan-

tum mechanics position and momentum are operators, whereas time is merely a

parameter.

The probability of a transition which conserves energy (i.e., En = Ei) is

Pi→n(t) = |Hin|2

t2

¯h2 ,

(6.214)

whereusehasbeenmadeofsinc(0) = 1. Notethatthisprobabilitygrowsquadrat-

ically with time. This result is somewhat surprising, since it implies that the prob-

ability of a transition occurring in a ﬁxed time interval, t to t+dt, grows linearly

with t, despite the fact that H1 is constant for t > 0. In practice, there is usually

a group of ﬁnal states, all possessing nearly the same energy as the energy of the

initial state |i . It is helpful to deﬁne the density of states, ρ(E), where the num-

ber of ﬁnal states lying in the energy range E to E+dE is given by ρ(E)dE. Thus,

the probability of a transition from the initial state i to any of the continuum of

possible ﬁnal states is

Pi→(t) =

Pi→n(t)ρ(En)dEn,

(6.215)

giving

Pi→(t) = 2t

¯h

|Hni|2

ρ(En)sinc2

(x)dx,

(6.216)

where

x = (En −Ei)t/2¯h,

(6.217)

and use has been made of Eq. (6.210). We know that in the limit t → ∞the

function sinc(x) is only non-zero in an inﬁnitesimally narrow range of ﬁnal ener-

gies centred on En = Ei. It follows that, in this limit, we can take ρ(En) and |Hni|2

out of the integral in the above formula to obtain

Pi→[n](t) = 2π

¯h |Hni|2

ρ(En)t

E*n* E*i
*

,

(6.218)

155

6.13 Constant perturbations

6 APPROXIMATION METHODS

where Pi→[n] denotes the transition probability between the initial state |i and

all ﬁnal states |n which have approximately the same energy as the initial state.

Here, |Hni|2

is the average of |Hni|2

over all ﬁnal states with approximately the

same energy as the initial state. In deriving the above formula, we have made

use of the result

∞−∞

sinc2

(x)dx = π.

(6.219)

Note that the transition probability, Pi→[n], is now proportional to t, instead of t2

.

It is convenient to deﬁne the transition rate, which is simply the transition

probability per unit time. Thus,

wi→[n] = dPi→[n]

dt ,

(6.220)

giving

wi→[n] = 2π

¯h |Hni|2

ρ(En)

E*n* E*i
*

.

(6.221)

This appealingly simple result is known as Fermi’s golden rule. Note that the

transition rate is constant in time (for t > 0): i.e., the probability of a transition

occurring in the time interval t to t + dt is independent of t for ﬁxed dt. Fermi’s

golden rule is sometimes written

wi→n = 2π

¯h |Hni|2

δ(En −E),

(6.222)

where it is understood that this formula must be integrated with ρ(En)dEn to

obtain the actual transition rate.

Let us now calculate the second-order term in the Dyson series, using the

constant perturbation (6.206). From Eq. (6.202) we ﬁnd that

c(2)

n (t) =

−i

¯h

2

m

HnmHmi

t

0

dt exp(iωnmt )

t

0

dt exp(iωmit)

= i

¯h

m

HnmHmi

Em −Ei

t

0

[exp(iωnit ) − exp(iωnmt ] ) dt

= it

¯h

m

HnmHmi

Em −Ei

[exp(iωnit/2)sinc(ωnit/2)

156

6.13 Constant perturbations

6 APPROXIMATION METHODS

−exp(iωnmt/2)sinc(ωnmt/2)].

(6.223)

Thus,

cn(t) = c(1)

n +c(2)

n = it

¯h exp(iωnit/2)

Hni +

m

HnmHmi

Em −Ei

sinc(ωnit/2)

−

m

HnmHmi

Em −Ei

exp(iωimt/2)sinc(ωnmt/2)

, (6.224)

where use has been made of Eq. (6.208). It follows, by analogy with the previous

analysis, that

wi→[n] = 2π

¯h

Hni +

m

HnmHmi

Em −Ei

2

ρ(En)

E*n* E*i
*

,

(6.225)

where the transition rate is calculated for all ﬁnal states, |n , with approximately

the same energy as the initial state, |i , and for intermediate states, |m whose

energies differ from that of the initial state. The fact that Em = Ei causes the

last term on the right-hand side of Eq. (6.224) to average to zero (due to the

oscillatory phase-factor) during the evaluation of the transition probability.

According to Eq. (6.225), a second-order transition takes place in two steps.

First, the system makes a non-energy-conserving transition to some intermedi-

ate state |m . Subsequently, the system makes another non-energy-conserving

transition to the ﬁnal state |n . The net transition, from |i to |n , conserves en-

ergy. The non-energy-conserving transitions are generally termed virtual transi-

tions, whereas the energy conserving ﬁrst-order transition is termed a real transi-

tion. The above formula clearly breaks down if HnmHmi = 0 when Em = Ei.

This problem can be avoided by gradually turning on the perturbation: i.e.,

H1 → exp(ηt)H1 (where η is very small). The net result is to change the en-

ergy denominator in Eq. (6.225) from Ei −Em to Ei −Em + i¯hη.

157

6.14 Harmonic perturbations

6 APPROXIMATION METHODS

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