MP463 QUANTUM MECHANICS Introduction Quantum theory of angular momentum Quantum theory of a particle in a central potential - Hydrogen atom - Three-dimensional isotropic harmonic oscillator Non-relativistic quantum theory of electron spin Addition of angular momenta Stationary perturbation theory Time-dependent perturbation theory Systems of identical particles
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MP463 QUANTUM MECHANICS
IntroductionQuantum theory of angular momentumQuantum theory of a particle in a central potential- Hydrogen atom- Three-dimensional isotropic harmonic oscillatorNon-relativistic quantum theory of electron spinAddition of angular momentaStationary perturbation theoryTime-dependent perturbation theorySystems of identical particles
REFERENCES
Claude Cohen-Tannoudji, Bernard Liu, and Franck LaloeQuantum Mechanics I and IIJohn Wiley & Sons
Examination (constitutes 80% of the total mark):duration: 90 minutes,structure: 3 questions, each with several sub-questions,requirements: answer 2 (and only 2) of the 3 questions in writing,maximum mark: 100 points.
Continuous Assessment - 2 quizzes (20% of the total mark):duration of each quiz: 30 minutes,maximum mark of each quiz: 10 points.
CHAPTER 0: THE POSTULATES OF QUANTUM MECHANICS
(From Cohen-Tannoudji, Chapters II & III)
FIRST POSTULATE
At a fixed time t, the state of a physical system is defined by specifying a ket |ψ(t)�belonging to the state space E.
The state space is a space of all possible states of a given physical system, and it isa Hilbert space, i.e. it is:
1. a vector space over the field of complex numbers C
|ψ� , |φ1� , |φ2� ∈ E, c1, c2 ∈ C (0.1)
|ψ� = c1 |φ1� + c2 |φ2� (0.2)
Definition: A vector space over the field of complex numbers C is a set of el-ements, called vectors, with an operation of addition, which for each pair ofvectors |ψ� and |φ� specifies a vector |ψ� + |φ�, and an operation of scalar multi-plication, which for each vector |ψ� and a number c ∈ C specifies a vector c |ψ�such that (s.t.)1) |ψ� + |φ� = |φ� + |ψ�2) |ψ� + (|φ� + |χ�) = (|ψ� + |φ�) + |χ�3) there is a unique zero vector s.t. |ψ� + 0 = |ψ�4) c(|ψ� + |φ�) = c |ψ� + c |φ�5) (c + d) |ψ� = c |ψ� + d |ψ�6) c(d |ψ�) = (cd) |ψ�7) 1. |ψ� = |ψ�8) 0. |ψ� = 0Example: a set of N-tuples of complex numbers.
2. with an inner (scalar) product.Dirac bra-ket notation:
So the Hilbert space is normed and a metric space. What else?
4. It is also a complete space so every Cauchy sequence of vectors, i.e.
�|ψn� − |ψm�� → 0 as m, n→ ∞ (0.12)
converges to a limit vector in the space.(We need this condition to be able to handle systems with infinite-dimensionalHilbert spaces, i.e. with infinite degrees of freedom.)
Can we be more concrete about quantum states? What really is a ket |ψ�?
Now, we need the concept of representation.Let us say we have the Hilbert space E and the basis
B = {|φ1� , |φ2�} (0.13)
and we have a ket
|ψ� ∈ E (0.14)
which we wish to express in the representation given by the basis B.We use the completeness relation
�
i|φi� �φi| = 1 (0.15)
as follows
|ψ� =�
i|φi� �φi|ψ�����
a number∈C
(0.16)
=�
ici |φi� (0.17)
Our state becomes a specific superposition of the basis set elements, i.e. we haveexpanded |ψ� in terms of {|φi�}.
What about a representation in a continuous case (e.g. a free particle)?
The completeness relation:The coordinate operator X has the spectral decomposition
X =
�∞
−∞
x |x� �x| dx (0.18)
where x are eigenvalues and |x� are eigenstates, i.e.
X |x� = x |x� (0.19)
Then the completeness relation is�∞
−∞
|x� �x| dx = 1 (0.20)
Coordinate representation
|ψ� ∈ E (0.21)
|ψ� =
�∞
−∞
|x� �x|ψ� dx
=
�∞
−∞
ψ(x) |x� dx (0.22)
{ψ(x)} are coefficients of the expansion of |ψ� using the basis given by the eigenvec-tors of the operator X, called wavefunction
Inner product in coordinate representation
�φ1|φ2� =
�∞
−∞
φ∗1(x)φ2(x) dx (0.23)
SECOND POSTULATE
Every measurable physical quantityA is described by an operator A acting on E; thisoperator is an observable.————–An operator A : E→ F such that
���ψ��= A |ψ� for
|ψ� ∈ E����domain D(A)
(0.24)
and���ψ��∈ F����
range R(A)
(0.25)
Properties:
1. Linearity A�
i ci |φi� =�
i ciA |φi�
2. Equality A = B iff A |ψ� = B |ψ� and D(A) = D(B)
3. Sum C = A + B iff C |ψ� = A |ψ� + B |ψ�
4. Product C = AB iff
C |ψ� = AB |ψ�= A
�B |ψ��= A���Bψ�
(0.26)
5. Functions A2 = AA, then An = AAn−1 and if a function f (ξ) =�
n anξn, then bythe function of an operator f (A) we mean
f�A�=�
nanAn (0.27)
e.g.
eA =
∞�
n=0
1n!
An (0.28)
Commutator and anticommutatorIn contrast to numbers, a product of operators is generally not commutative, i.e.
AB � BA (0.29)
———–For example: three vectors |x�, |y� and |z� and two operators Rx and Ry such that:
Rx |x� = |x� , Ry |x� = − |z� ,Rx |y� = |z� , Ry |y� = |y� ,Rx |z� = − |y� , Ry |z� = |x�
5. A is selfadjoint if A† = A.This is the property of observables!Their eigenvalues are real numbers, e.g. X |x� = x |x�
6. A is positive if �ψ| A |ψ� ≥ 0 for all |ψ� ∈ E
7. A is normal if AA† = A†A i.e.�A, A†
�= 0
������������������commutator
8. Let A be an operator. If there exists an operator A−1 such that AA−1 = A−1A = 1(identity operator) then A−1 is called an inverse operator to AProperties:
�AB�−1
= B−1A−1 (0.46)�A†�−1
=�A−1�† (0.47)
9. an operator U is called unitary if U† = U−1, i.e. UU† = U†U = 1.
Formal solution of the Schrodinger equation leads to a unitary operator: if H isthe Hamiltonian (total energy operator),
i�ddt|ψ(t)� = H |ψ(t)� (0.48)
⇒
� t
0
d���ψ(t�)
�
|ψ(t�)�= −
i�
� t
0Hdt� (0.49)
If the Hamiltonian is time independent then
|ψ(t)� = e−i�Ht|ψ(0)� = U |ψ(0)� (0.50)
10. An operator P satisfying P = P† = P2 is a projection operator or projectore.g. if
���ψk�
is a normalized vector then
Pk =���ψk� �ψk��� (0.51)
is the projector onto one-dimensional space spanned by all vectors linearly de-pendent on
���ψk�.
Composition of operators (by example)
1. Direct sum A = B ⊕ CB acts on EB (2 dimensional) and C acts on EC (3 dimensional)Let
How is the wavefunction φ(p)(p), which describes the ket |φ� in the momentum rep-resentation, related to φ(x) which describes the same vector in the coordinate repre-sentation?
φ(p)(p) =�∞
−∞
�p|x� �x|φ� dx =1√
2π�
�∞
−∞
e−i�pxφ(x) dx (0.100)
φ(p)(p) is the Fourier transform of φ(x)
φ(x) is the inverse F.T. of φ(p)(p)
φ(x) =1√
2π�
�∞
−∞
e+i�pxφ(p)(p) dp (0.101)
(Cohen-Tannoudji Q.M. II Appendix I)The Parseval-Plancharel formula
�∞
−∞
φ∗(x)ψ(x) dx =�∞
−∞
φ(p)∗(p)ψ(p)(p) dp (0.102)
F.T. in 3 dimensions:
φ(p) ��p�=
1(2π�)3/2
�e−
i��p·�rφ
��r�
d3r (0.103)
δ-”function”
1. Principal propertiesConsider δ�(x):
δ�(x) =� 1� for − �2 ≤ x ≤ �20 for |x| > �2
(0.104)
and evaluate�∞
−∞δ�(x) f (x) dx ( f (x) is an arbitrary function defined at x = 0)
if � is very small (� → 0)�∞
−∞
δ�(x) f (x) dx ≈ f (0)�∞
−∞
δ�(x) dx (0.105)
= f (0) (0.106)
the smaller the �, the better the approximation.
For the limit � = 0, δ(x) = lim�→0 δ�(x).
�∞
−∞
δ(x) f (x) dx = f (0) (0.107)
More generally�∞
−∞
δ�x − x0
�f (x) dx = f
�x0�
(0.108)
2. Properties(i) δ(−x) = δ(x)(ii) δ(cx) = 1
|c|δ(x)and more generally
δ�g(x)�=�
j
1����g��x j�����δ�x − x j
�(0.109)
{x j} simple zeroes of g(x) i.e. g(x j) = 0 and g�(x j) � 0(iii) xδ(x − x0) = x0δ(x − x0)and in particular xδ(x) = 0and more generally g(x)δ(x − x0) = g(x0)δ(x − x0)
(iv)�∞
−∞
δ(x − y)δ(x − z) dx = δ(y − z) (0.110)
3. The δ-”function” and the Fourier transform
ψ(p)(p) =1√
2π�
�∞
−∞
e−i�pxψ(x) dx (0.111)
ψ(x) =1√
2π�
�∞
−∞
ei�pxψ(p)(p) dp (0.112)
The Fourier transform δ(p)(p) of δ(x − x0):
δ(p)(p) =1√
2π�
�∞
−∞
e−i�pxδ�x − x0
�dx (0.113)
=1√
2π�e−
i�px0 (0.114)
The inverse F.T.
δ�x − x0
�=
1√
2π�
�∞
−∞
ei�pxδ(p)(p) dp (0.115)
=1√
2π�
�∞
−∞
ei�px 1√
2π�e−
i�px0 dp (0.116)
=1
2π�
�∞
−∞
ei�p(x−x0) dp (0.117)
=1
2π
�∞
−∞
eik(x−x0) dk (0.118)
Derivative of δ(x)�∞
−∞
δ��x − x0
�f (x) dx = (0.119)
−
�∞
−∞
δ�x − x0
�f �(x) dx = − f �
�x0�
(0.120)
THIRD POSTULATE(Measurement I)
The only possible result of the measurement of a physical quantity A is one of theeigenvalues of the corresponding observable A.
FOURTH POSTULATE(Measurement II)
1. a discrete non-degenerate spectrum:When the physical quantity A is measured on a system in the normalized state|ψ�, the probability P(an) of obtaining the non-degenerate eigenvalue an of thecorresponding physical observable A is
P (an) = |�un|ψ�|2 (0.121)
where |un� is the normalised eigenvector of A associated with the eigenvalue an.
2. a discrete spectrum:
P (an) =gn�
i=1
�����ui
n|ψ�����
2(0.122)
where gn is the degree of degeneracy of an and {���ui
n�} (i = 1, . . . , gn) is an or-
thonormal set of vectors which forms a basis in the eigenspace En associatedwith the eigenvalue an of the observable A.
3. a continuous spectrum:the probability dP(α) of obtaining result included between α and α + dα is
dP(α) = |�vα|ψ�|2 dα (0.123)
where |vα� is the eigenvector corresponding to the eigenvalue α of the observ-able A.
FIFTH POSTULATE(Measurement III)
If the measurement of the physical quantity A on the system in the state |ψ� givesthe result an, the state of the system immediately after the measurement is the mor-malized projection
Pn |ψ���ψ| Pn |ψ�
=Pn |ψ����Pn |ψ�
���(0.124)
of |ψ� onto the eigensubspace associated with an.
SIXTH POSTULATE(Time Evolution)
The time evolution of the state vector |ψ(t)� is governed by the Schrodinger equation
i�ddt|ψ(t)� = H(t) |ψ(t)� (0.125)
where H(t) is the observable associated with the total energy of the system.—————-Classically