PHY3001 : Lecture 3

5.Dani / ish in

19 Sep 2022
Contents of the lecture 1
1 .
How to deal with
quantum systems ,
whose SE we cannot solve exactly ?
Perturbation Hamiltonian Ñ Ñ◦
'
-
and zero -
order Hamiltonian
-

Finding approximate solution to a

perturbed SE with time -

independent perturbation theory

- 1ˢᵗ order perturbation theory E and :
"'
T
"'

- 2ⁿᵈ order perturbation theory : E '"

Degenerate perturbation theory
-

Variational principle for

2 .

finding unknown
ground states
A Appendix about identical particles and QM in 3D
perturbationtheory 2

Thus far we considered a

very rare examples of potentials ,
for which one

can
exactly solve Schriidinget equation
particle ✓ 1×1=0
}
a) Free
→
Square wells
b) Constant potential V41 -1
c) Harmonic oscillator F( x ) & I2
d) Spherically symmetric Coulomb potential ✓ (1) ✗ f- [see CL4 in Gr]

How deal with real systems that solved Our lecture

to cannot be
exactly ? →

today
step-by-step procedure :

1) Find the closest exactly solvable system with Hamiltonian Ho : Ñ◦4°= EE4P
"
2) Express the Hamiltonian in
question Ñ◦ plus perturbation as
" "
H that is
"
much
smaller " than to ,
i. e. { ti > ⇐
'
< it >
.
:

n Here c- is a dimensionless tracer of smallness (in the end c- =D

It ≤ [I of
,
(1) + EH Orders of smallness will be equal to powers c- .

3) Assume that perturbed eigen functions 4h

" "
be expressed can as an
expansion :
(due to linearity of SE ) : 1ˢᵗ order ⇐ order
↓ ↓
(2) 4h T5-1HE + EYE = -1

Ñ
. . .

and eigenvalues of can be

similarly expressed :

(3)
En=Ei+eEi+ÉEn± . . .

4) Put equations 4) (2) and (3) ,

in the SE
,
TT4N =
EN4E and collect terms with
the same power of c- .

E¥=m_p¥
: Perturbed ISW
H'G)
{ 0 ◦< ✗< a
-

-2m
+ V04) , % = -
,
otherwise
•

" ""
,
" "
0 ,
otherwise
"

Ei=ᵗÉ → =
"
Ei Hittite > £ / d×sin4 =

a /2
D= ¥

4i=£sin( × )
 ETI )(Hit E4E
' 3
/ ( Ei EEI E2E? -1 ) ( Hi-tech
'
242-1 4¥ )
'
+
+ c-
= + + + c-
. . . . . .
.

terms at of gives
collecting c-
.

powers

14a) : It ◦
Yi =
EY4E -
zero order
titi Fifi
"

titi E
'
1461 E : + =
+
°
-

first - order correction

n u

(4) C-
2
: ti.fi tiki + =
Eiht Eiuu + EE43 -
second order correction
-

solve the above equations sequentially substituting the lower order solutions ,
-

into the next order equation as known functions .

→ First order -

theory
simply multiplies 14 b) by 144
"
To find first order correction to the levels one
energy
-

or in bra ketlaug.ua#ffrmtneTeft and calculate the resulting inner

p ro d u c t
-

<ÉtiMi > + trillion > =

Either >
'
+ Ei<ÉÉ>
EEÉ ↓
EnÉ + tutti 't:> =Eiw + Ei

Hence we
get for the 1ˢᵗ order correction to
-

energy of perturbed system :

(5) Ei-v://t.ir:>

Mainte.su#: 1ˢᵗ order correction to the energy the expectation value of the
-
is
perturbation ,

in the unperturbed state .

→
c-rrectit-theeigenfunctionsj.si me {1%7} is a
complete orthonormal basis ,

one can
express 141 > as a linear combination of them 4h =
cilium
m≠n
coefficients in' show how the of the ¥:)
-

large is
projection perturbed n -
th
eigenstate
on the orthogonal direction of the m - th unperturbed eigenstate hi ,

To find a let's move all instances of 14h > in 146) to the LHS of the equation and all tri > -
s
, ,

multiply the entire equation by 4%9 from the left

to the right ,
and :

Gilli '%%E!
{
° it k=n, since
ti )y; >
4h42 (Hi
' >
-
E :) cii ' hi> =
< qiKEi - =
-
< Titties> = -

HI if k≠n
. ,
n≠m_ → 14¥
trivial of 0=0
For k=n , we
get a case

For k≠n , we
get : of
E ;) filth
' '
diagonal matrix element
Non
ci:'( EL
-

-
= -
< Yi > = -

then ← perturbation energy in

the
unperturbed
eigenfunctions 14ns basis
 Recall that these coefficients show the amount
(6) [ [
'
=
É≥ ,
n≠k the perturbed state 14h> projects on all un -

( EE -
E;) perturbed states it:3 orthogonal to the 4
unperturbed state Ifi> i.ec Nitti> ,
=

The above result is safe

long each En° has exactly one (f)
corresponding
so as

eigenstate unperturbed spectrum degenerate ! 45 ,

ie .
energy is non -

Else, if 2 eigenfunctions If;) and ITI > share the

, ,
, same
energy ie ,
.

EI EE2 coefficient
=
,
Hittites deal with it
)
,

( we
"
' %
(6)
Fit
=
→ -
later
Our result for 1ˢᵗ -
order correction to
eigenfunction reads :

4mi / ti / Fi >
'

(7) F. =
hi
m≠n

→ Second order -

theory
To get EE ,
let
again multiply 14 c) by Cyril and calculate the inner
product
EH0H ◦ (
remember
n≠k in (5) f) 1

Giffen >
-
+
Hittite : > =

-
EYE> Eire: > Eiji> + +

Ei=< viii. =¥,ÉiÉ=Éi

Hence
(8) Ei=ztp
Ei Ei m≠n -

{
✗ ✗ '× a) ◦< ✗ <a V41
Example
- -

ISW with parabolic floor ✓a)

,
:
,
i. e. =
- otherwise A
,

Here we have H◦= -

ʰÉ¥✗ + V. (x ) where ✓◦ 4) = {% otherwise

◦ ≤ ✗ ≤a with E- afsin'x)
, >

◦< ✗≤ a

E! =
and H' guy,= =

1-2×1×-4
0elsewhere
,
,

dÉ( f- Énp )
a

E! = < WH
'
Ii > = -
dxsiil ×
) xx -
a) = - +

◦
a

'VE >
¥ f.dxsinl"¥x)sin( ) 7
41=-24111-1
k≠nEq) 4£ <tilt'Yn% -
× ✗ (x a)
-
= ◦

with odd n
a

correction to the Yi
has odd
{ ¥¥÷k+u if ktn is only cii
'
≠0 whereas
4da2kn( 1+1-1 )ʰ
even ,
,

= =

odd for even in 49 has first order

⇐ (K2 NY12
-

L 0 if is
correction even K only

YEIH.IE?---fFIIE-xi--iii.w---EIfnaI-wp
,
if k+n even
.

'
di --
,

0 if ktn odd
,

/ < %° / H " >

" 1282296 K2H2MZ
for k+ "
E?
even
=
I =
11-6-42 (na ha )5 ,
KEI Ei )
-

k≠n
-

.
 5
Degenerate Perturbation Theory

Consider first a case of two-fold degeneracy ,

i. e. when there are
2 distinct
states with the É then consider excited states
4L and 48 same
energy , eg ,

of
hydrogen atom where
, ,
e ,

states with different orbital

Ñ°%° Ñ°%°
◦
=
E°4a° ,
=
E-
f.
°

,
4%1%7=0 momentum e. have the same
En,±E En
energy Eng
: =

,±e
and any linear combination of these is also an
eigenstate of Flo :

(9) 40=241 + P4E Ñ°y◦ = E°yr°

ti typically lifts
" "

the
degeneracy the perturbed
'
Perturbation ,
→ states will have
Ei- E
different energy levels where the larger stronger the perturbation
☐
E-
◦

f. E- is is
☐E , gap

;f¥¥g:[I ¥ ¥; %)
into '
Perturbed eigenstates will also split from + but not "
°
""" " "

good states Hydrogen

atom in
magnetic field
,

calls
"
combinations Griffiths "

YI and % but rather into their

,
,
, ,

,=→É
"
,
Zeeman lever splitting
^
E Multiplying
↳
146 ) by <µ:/
gives :

µ
BE + trait '4°> t = + EY49 V7
→
""
"
% Using (9) one
gets
:& #
,

tip; > patil titi >

E-
¥
'

:/ + = ✗E
◦
Perturbation - -
strength
Waa WA6

Through similar steps one

gets for <+it :

'
BW66 =P E ✗ Wba +

The two equations above be simultaneously satisfied only for

can

certain
✗ and p that appear to be components of eigenvector of an

ti
'

a matrix ☒ that consists of matrix elements of in tuoi > and 1%9

" )
°
[
Waa Wat

www.b ][{] = E' [I]

those that
'
matrix V.V
✗
, p and E are
diagonal ise :

det.IN ] (waa E) ( Woo ) Was Wba

' '
-
E II = - -
E -
= 0
 which has 2 solutions . 6

EE-IL-waai-wu.INT#Ff-
This is a fundamental result of the
degenerate perturbation theory
that describes splitting of degenerate energy level under the in -

uence

of perturbation .

Corresponding ✗ ± and P± can be found

by substituting EE in
110 ) and
accounting for normalisation condition 1×12+1912=1 2
:

(waa -
E-f) ✗ + +
B+Wab =D and 12+12 + If / = 1

f-
Wat
Ef eigenvector :
[ §;] = 1
Nt -
Waa -
Ei ] .
N+=-tET
Similarly for El gets
/ %/ # [
% E!
]
one
-

N_=fft+a
-
,
,

Wba d- +
( Woo -

E) B- = 0 =
-

Wba ,

ut.findnewenergyieueisonene dst.diag.ni sethe@m.at

To
- summarise

a) Perturbation makes degenerate energy levels split

4-1=2+1%+9+48
En±ew = E° ± EI f. →

4- = d. Fit B- Too

rix of perturbation in the basis of unperturbed

energy
< YF1H
degenerate eigenstates Wij =
'Tj° > where i,j= a ,b
,

basis of
c) The new energy eigenfunctions is defined by
solving for eigenvectors of
Wij → ✗ ± and B±

H-ighei-orde-d-egeuera-y.tl
What if there are more than 2 eigen functions that have the same

energy eigenvalue ?

for the two-fold

Answer is Use the
evident → same technique as case

(degenerate eigen d)
upto number
Just increase dimension of Vvij accordingly i. i. j
,
e. = a
,
b. c. d. . .

functions
-
E-xamp.ie : Particle in an infinite cubical well 7

gz
2 <
0 ◦ <✗
if a

Unperturbed potential :\;y 2)

>
,
is =

✓ •
,
+ no elsewhere
,

3D
Schiodiugerpzequation in this case :

(ÉÉy+)4HyH
-
+
VK.yhkx.gr/--ET
☐
2 -
Laplace operator
Solution this of
in case is simply a
product
%
3 infinite
square well eigenfunctions
F. ( if F) (1)
✗ =
sin / ' ✗
× ) sin (tansy ) sin (¥22) ,
nx
, ny ,n≥
-

integers

Energy eigenvalues are

given by expression
42*2
( h HI ME)
°
f- = + +
nxnynz

Ground with n×=ny=uE1 not

state is
degenerate :

E: =
E%={ᵗm ,
and II. =/I )% sin II. ×)sin( g) sin /E. 2)

is 5-fold
First excited state however ,

64211-2
, degenerate :

EI EL2 with
E EI corresponding 4h _=% 4=71 4=-41
= = =

, ,
-2mA≥ , ,

I
{ V0 ◦ < ✗ ≥ <

If we now introduce perturbation potential H' = , if

0 elsewhere
,

situation
"

will
"
we
get a lifted degeneracy .

Let's apply perturbation theory to the 2 above states and find new
energy
eigenvalues %, a,
44 at≥ %

Grouudstate =FaPK↑d×s)§dysEt)fdzs4-
: E
'
=
thallium ,
>
0

pert ) f- V0
°
=
( raised by % of the

t-excitedstate.VE % ¥12
.

Wig . =
44:/ Ñ' %? > ,
where i,j= a ,b,c

Waa=Woo=Wu=FaPK§d×s¥ᵈÉ Édys¥)Jd
a/
a/ 2 4 a/
2 %

0
≥ sift ) =
¥
Non -

diagonal matrix elements : 3¥ 9/2

5¥ % 8
a/2 912

Was = < 4%11^-14,2 > ,

=

Fad×sinP¥Én)§dysinl¥)p )↓dzs"E) =§÷¥

All other off the and equal to Nab
-

diagonal terms are same

]
" "
Wat
THE ≥ ¥
-
K
l
K
k

1
,
☒ ≤
waa
=

(¥] ≈ 0,61
'
I -12k}
Eigenvalues of THE read E
a.6,2
=

¥ {T -
K
,
I -
K
,

Is:|
-

Eigenvectors
which
:

the
a
II. ftp.f-EI?I.fE:f- ¥11 ]
b

means new
eigenstates ^ ^

:|
E
E- £4:-& :) ; %°=f=( % -9:)
.

¥ (4%+4,1+1%2)
. _

4?
.
.

= ¥" "
"
E? iIÉ
again degenerate _ _
.

Varo±aprple= -

extremely useful for finding ground state energies

in complex potentials

the
The upper bound on
ground state energy can be estimated as :

Egs≤L4IÑl4=)
where it
the Hamiltonian of
is our
system and 14> is !
any 1 )
function of Hilbert space .

Indeed ,
since 4=-444 where ÑYn=En4n ,
,

einen truth> ≥ lent

{Zeman / [ cnyrn> -2
=
hence 1=2414> = =

him
and (1-1)=4%4 / HE cut > CEE.cn thick> =EEnknF =

Egs [ lent
'

[ Euknl ≥
Egs
= =
 At
Appendix : QM in 3 dimensions and identical particles

Real quantum spatial dimensions theirfore have to be described by

particles can move in 3
, a

whereas the wavefunction naturally depends

3D
Schiodinger equation ,
on E- { × , y , ≥} and time

'
t
it d[Y = -

Em
☐ 24TH + ✓ (F) 4(F)

Here we
generalised momentum operator f×= it ¥ -
to a 3D version ,
ie

f- =
{ pi.py.pl} = -
it { ¥ }-y I} ,
= -
it J
,
,

where
J=£é+¥é ,
+
£É is a
gradient operator
¥
and ☐
2
= ( E. F) =
¥ +
¥ +
222
is a
Laplacian operator
All quantum properties we derived for a TD -

particles apply equally to a 3D case

system of 2
particles
Consider a situation when there ,
is more than one
particle .
Like for instance 2 electrons
, ,

in the He atom .
Each of the particles has its own spatial I and I but since
coordinate , ,

nucleus for instance) they share the wave function which

they move in the same
potential ( of a ,
, ,

has to satisfy the joint Sahriidinger equation :

ih-dtff.FI#-=-Em.q-v-I-mP2-f-V(rT.ri)I
"%
-

ICE ri.tt-yrfi.ES e-
,

I Em 0,2 £ Uri I)
~
'

HY1E) =
EYRIE) ,
and = -

,
_

2m29
+
,

Non -

interacting particles :

In the situation ,
when the particles a re not
interacting with each other
,
but may
be both under
the action of external force then the potential is and
some ,
just a sum :
VII.E) =
HE )+Yri) ,

the joint wavefunction HE ,I ) factovised the Sts for the two

, can be and
particles can be
solved independently 4th %)
: =
fair ) % (E)
.

, ,

In ,
F. (E) 0,2%15 ) -

Emirati)E%(E) +
41%1%(51%15) +
4th) Ya II) 4ft) =
EK1E) #-) / : E. %

f- hÉ☐i¥!Éˢ v.li/I+EEiiYEYE'-i-YriH=E
+ E- Eat Eo

FHÉ EÉ
.

2¥ 0,2%151
,
+
viri ) Yali ) =
Eayralñ ) -

¥-2924b III +
YIl%(E) =
E6 4LE)
Identical particles .
Bosons and fermions A- 2

In QM there is no to tell apart 2 electrons or 2 identical atoms from each other

, way , say ,
.

However the above

quantum state of 2 non -

interacting particles does

distinguish particle 1 from

that
particle 2 :
yah E) ,
=
fact ) f. (E)
.
-
we know 1 is in state Ma) and 2 is in state / %>

In reality all ,
one can know is that one of the particles (whichever) is in ya>
,
while the other is
in / To > .
Therefore in QM ,
one has to construct a wavefunction that cannot be used to tell particles
apart .
There are 2 possibilities here
,
either to make the wavefunction completely symmetric in

respect to the swap

of particles ,
or
completely anti -

symmetric :

ftp.ri ) = A [ Yati )%(%) +

% (F) Valid ]

It that that allow

happens so
,
particles symmetric wavefunction are
very
distinct from the ones

with anti symmetric -

one .
The former called bosons ( as they follow Bose-Einstein statistics and )
the latter are called fermions (they follow Fermi Dirac statistics) -
.

Bosons have
integer spin whereas fermions always have half
,
integer spin Finally.

,
all
the solid matter is made of fermions because of the peculiar property they have due to
the anti symmetry of wavefunction Pauli exclusion two fermions
simultaneously principle
-
: -
no can

quantum expression
be(F) in the same state ! Indeed ,
if in the above Yahi ) f. =

then III. E) =
Affair) Yatra) -

Yalri )4alñ)] ≥ 0 -
non
-

physical !

Due to Pauli exclusion electrons cannot occupy the same energy level of the atom
principle , ,

so far as
they have different wavefunction It is also responsible for the degenerate electron
.

that does not allow white dwarf stars to collapse under the
pull of
gravity (Gr 535 )
pressure
.

To summarise the ,
following is true for non -

interacting particles :

Distinguishable particles : TIE E) ,

=
Tati )%(%)

Indistinguishable bosons : Tai , E) =

¥ [ Tati) f. (E) +
F. (F) Talk)]
Indistinguishable fermions : YE > E) .
=
¥ [ Yak) f.(E) -

F. (F) talk)]