Breakdown ofclassical statistical mechanics.

In classical picture, probabilistic description

the

ofobservables are derived from I'm

parliation
function of classical
funism, which a
is
a

Hamiltonian, H(9, ).

However itturned outthatsome predictions

classical picture with
using were not
compatible
observations.

Some such cones were,

1. Heatcupait A diatomic undercla

Heat ofsolide.
2.
campantly
3.
Black-body radiation.
 For diators undecals, in classical picture,
we assume a
hamitowa for a
simple molecule,

2,:+ Et V(--9).

and the single particle partition function,

2,: Jadade e-B*

h

At dilute limit, one can assume I'm

particle are

idea-you like, and Eve z,

calculate avenge evens,

((zr),
F:
If one
the

one obtains. I.
I best,

and Cr.
: Eks
However observation,
in this value is observed only
atthe
hightlimit
 Cr

-
·

temperahm,
I
Atroom
-

, 3/2

3 book look
at += c83, th
5/2
En
T 10

to
explain experimental
the observation, one

mechanical for
has to include quantum description
viberate and rotation.

Forvibration, consider quaturn harmonic oscillater

Hamitra, it:S4+YTue.

Se(n+Y)
twe -

pliue/
and, 2:
Fea S
In the limitof in
Gr matches the
Bio,
classical picture. &

cr:(-((z)]
·
 Rotational description,
In Quntum mechanics,

Serf:
test). (21,
↓

PArt. degenerney.
Zrt.=e- ->
Provids do due rotation
to

·zsn
↑+ 12 + V
Y
-

s - -

3/2
IT.
T 7
300k 1000k

Atnight. Or has contributions forms translatet

rotct+ ubrate
mode.

atboat. Or has contributions from translatent

rotations

atSmallt, from translation

is
only
 ofsolide.
2.
Heat
capacity
Simple picture, solid ations are arrayed on

of them
a
lattice, as each

X -

can be treated on 3-d indiulat harmonic oscillation.

Hr:(then Ithe given Coweaptas

i t
o,

Howesul, Car +
experiment,
in a - 0,
+

Modified picture, consider system ofcoupled

a

oscillate

to
them, ithas different
frequencies correspond
differentwound mode, no
2
(m).

H [(n++ (twe(k)
=

7
to obtain (i
k,x I

correctbehaviour.
 3. Black
body malici 1

..
-

Model:E and B wame

murder inside a
box,

ich
it (m,ca)-e)

for
Building the statistical mechanics
description
quatur -
systems.

the
fundamental difference between classical and

quatuan systmes;classical observables are determinatio

while
quantum observables are
inherently publicis

Classical microstate; state rector, [9:, Pi3.

phase-space.
in

& nantum microstate:State vector is Hillertspans.

(1) (n14), (2)

A in
147:
Dirac mitatin The bane verb.
 Galt) a
in
complex coefficient

Ifwe choose coordinate buis,

(99.314):4 (e.,..... (r).

condition,
Normalization
(214) 1
[4H):[[412)
=

whin, (t) (214)

=
*

I
complex comjujets.
In coordinate space, (id.14 (8,...) 1
=

-
 Observeldes:

observable have defrut

In classi sybm,
value
plaque
in
0 0(:, ).
=

bracketrelati
P.and 9, follow the prisson
[0:,9;3: -
Sij

In 2.M, p and I operator,

are

[P,5,] 8-- = itdis

Ia.m, I, the observable an

in

operator materia?

In fanation ofE.B
gewerd, the observable, which a
is

can be
eapened
an OC, 5).

observable does nothave

Unlike classical
a

sylum,
value' OZ
defuh value, butan
'expectation
<O) <41014):
:

24012)(-14)
 In
esagle,
SUCES: Side:4* (:.,...aw) U(91) +(9,,. [r). ...

and (BCPC):J.d* 4*(a. (i inz) y (G., .... Yr)

...

The observable [0) should be real,

SO): E4123<a101m) (m143

Din Hermitian, 0:Ot

where, (w10(v)* (m10th)=

Time
=>
erdulim in
classical symme

:
-

In Q.M,
it,14]= 14)
2

Letthe Jane (n), diagondies it.

HERE, (n2
14: [[w14) (n).

in
[2/4) E(1/4)
=

-
=
Ot
[alt):
E (elt),
Ent (n)4(0))
set
-

snationmasostate enemble
the ene
an observell 0(9,P):0(gr):[P(na) 0(ka)

-JTIdd: 0 (9,4) 9([8, i))

= ([0,3,1) EPTs(a: -9,)

=

S'(0, -n()).
In quator syban, 9/4)] the
is set ofpossible

state, with a
probabilly da
 [07 [is
=
<4,1014)

Sun Pr(tslm) <m10(a) (n1 tw)

=
[(m10ln) [Pa[al4) (4, land
m,m

[M101) (a19(m)

<ule(m):[Pa[nl4u) <talm) is in
where
x

I
Deadly matrix

In im banis
independentform
9:SP 14s)<tal.
-

28:
(wle(m) (m10le) =
 Properties ofthe density matrix

) ullm) SPs[elStslm)
=

Tr(e) E(ulelz) SPs[ula) [4,12) =

=
=

=SP ((2+)1 5 =
=
1

↓
-

I
Normalization
Hermiticity.
-

2)

*
Culeton):(mle(n)

sclet/m): [(214) <41m) Ps =

3. Postinly,
<9/119): [% (9/-) (19) [001691-3/
=

20
Positive definit
 Time evolution,

classical statistical know,

In physics, we

:EH, 13:t it- t.

Dou
quantuan stat. plys,

[P,/4(11)
f(x) =
(4c+1)

(4gC)
=it "a(s))
it

We know thati t /4):H143

,
and -it
, 4):44/77

of:SPs(it,
it (a) [4al 14,7 +

it [41).
(4,(4,) H)
=\4(((,)(ts)
-

=[P(n+ (4)24,1) -

[P614a) (t,/1).
H,e)
it
I:19-92
 condition,
I [1,1)
Equilibrium 0
=
= =
0

function of Ct.
salidly if I
this in a
in

Sais realm.
We are
free choose
to the

be the
to
one can choose the basic vectors

fundin of
states of27. (Since I in a

eigen H).

fam:(n191m) will have

only diagra
element

fam: fum.

thicrocanonical ensemble.
-

Ia classical stat. mech

E =

iitnice."E
 mismocaonic ensemble,
In
quantum
fixed.
N in fixed, X isfind, is
I

a ccessible ministel
E):total number of

Energy'f'
with

<clem)
StefanEm
=

element
-is
digond materia, with
a
mounzero

having agamalues ofEn: E

Firstcondition, -
Equal Appioei equilibriu
probability.
Second conditi sandra phone.
=) Independent
mei, 9:0

(214) eidefal=

S4/m):citm(a).
Ede
:(9m-9) (al
SP: <el43<41m7
:

~ Sun.
 ensemble.
⑳Canonical
fixed.
T is fixed, N is fixed, X is

(B)
e
=
(19(m) [(u)e**
=
(m>.

In choose ejenslots
I'm
quantum mechanics, one
can

H(m):Em 12).
which
digamales. H.

fam:I :et
Z

We know that Tr (fu):1, See: E

z:Tr (f) =
Set
-

Grand camona ensemble

-

inCe-***)
P(B, a)
ear),
=

a:

ez(P)
-

V0
=
 Particle box.
Example: in
a

* Consider a
periodic foundry condition,

where dos ofU periodically repeated

a is in

all directions.
Salve

I
itin

P, P:-ity coordink
H:
space.

H: -
22
-
2
Sm

Energy agen stat, 29:E9

: , es 3 grandin
9:
ware
F socia

Figawhe E(2):
Ih5:Enx, my, 223
n 0,1,12,...
=

qn)
 matrix I,
Compete deadly the

coordinal fami (xilf, (n)

to
expressed in

fair which it in
It convenientto
is
use a in

diaysad. (Every eigen stabl Em: 2 m.

3:
[Ciln) enY((a)
z

z: Septimism. When island,

:2π
I
is

vid-Pla
e I become ermlines
I = 2

sa

. Iken)
=v.

(ambes):
converted
Similarly to calculate, Sam over is

integratie:Vdn
il**e-Ph"/m
into an

(2A)3
 v/dn e-PH"/m I
-i(x x) 2:
/y
-

<ilek): -
C

(2A)3
-

(e-iCo-i)-pnYam.
=

:text
 Hilbot for idential
particle.
space
classical Gibb's
For
system, parades was

removed factor VI,

by dinding by a

number of
the
permutations.

However, in classical
system,
it is
still
possible
to 'tay' a
particle
and follow its trajectory.

So, even all the feature are same,

one can

Consider such
particles as
distinguishable.

In
quantum mechanics, itis not
possible to

trach' calculat tim

a
particle precisely, only
pandabilities.
the
probability for two
particles,
14 (1, 2) R defined
is
by In two
police
Wave fundin
 14(1,2)1 14(, 1)12
=

This gives
two possibilities,

14(,2)) 14(2, 17) =

and 14(,2)7: -14(2,1)

↓ I
chars in
No
change sign
under
Syn
permalit under

permeti
For an of
particle system, N! permutations
are
possible.
possible
series ofa particle
Any permutation
a
are

exchap. For example,

for 0 Y
=
I 234 - 32 14

32
S
Parity ofa permutation
Peamatalin I
operati,
defined
Parity ofpermutation
us
in

E
if P in even

(1)*
+ I
=

- P
If is odd

Since 14(12)):1(4 (2,13),

thatt hem as

quartner mechanics
postulates
2
types ofparticles,
under enchage ofparticle
)
Fully symmetric
an

Bosomes
14(1,2)) 4 (2,13)
=
=>

as
fully antisymmetric Fermiones.
=>

For 's' particle,

Bosoms, 14(2, ...0)] +
= (4), ...

v))

Fermion (4(,2, ...)) =

(1)P(4(1,2...r))
 Constructing symmetric
and
anti-symmetric
State renders

Inc.
(14
x
particles
14
+

(n(ix)= ((4(ix) 1(2,4) -

's'
Fur
particle,
), ...)
14(1,..071= (
different
all
if
particles have
states.

14...w. =

(SEP(4C, a..)
 Hamiltower ofidentical particles are
symmetric
under permutatio
Hildat
For non-interaling system, the product
on
ofone body
space is a
multiplicate
(0).
15,5... krx 14) (E2)
=
. . .

I coordink repramentalis
(i E, hoxa).
↳, a ... oh, i ... "re
and it
1...nb=(E) in.... inte
However,
* thisdoes satisfy
not the
symmetry
ofthe state.
propertin

The fermionic subspace. (ambisymade).

In...im?=itSt"915,..nw)

--(-(3,4)}r=
Exaple (bi, ii)
1!
E:appears on than once, the resultiszero-
 Bosonic subspace,
15...5) .*
=
(ni,..in)

Far a
particle, 14; r): (14,2) +
(4, kD).
restriction for allowed values of
In this care, no
I
k

particle
can

So, N+=N! Since a

falicular one

in v'tin!
repeated
is
lime. Ne=

three Bosonic state

For example, if
a
particle
is constructed from two one
particle state (a) and one

stat
One-particle B.

1x(P) + (2xp) =
+

12P)) 1Bxc) + +

164).
1)
+

vE
1pac>
=14(a)
+

⑮
 In gewed, I1Y ++
=

Booms
y =

y: -1-Fermions.

"*(E3)
Isnk,: >

quarti
is sin e dby
a

Each stud

number
occupany
the number ofparticles the a sick
me
in

Camonical formulation for bon.

particles
a
-many
in

Denaily materia for

particle
(95'3/919537

=EST"
↓
Epl
* o'SS(K

restricted sum.

In
Win!
t
* Restricted such need to
be converted to

full sum,
by multiplying by appropriate
factors.

resultantsum,
has to
To
*
integrate the she

emply inverse
permutation p' and followed by relation

permut 's'
(, vi)
(N c)
-

One
*
yet an entra term =

e e
/

which
being in an
action, which is
purely
mechanical ..., the has be
quarbour system to

treated like an
particle.
in

I
can be calculated from Tr
(9), from Silsil)
 Instind, calculate
to , one can
expand
7
eigenvekler
in
space ofEr

+(1) [ <n182)
=

\E3
=

Eep-P(,s(rs)
the
due to
this restricted sumes will difficultto
perform

assets occupation
Sun over
the
convert of
number

number, for Fernion

Sec.
1
is
Occupany M 0
= or

Y 0, 1, 2
=
... For Brsons.

N how
particle system me
gives you may particles are

in a state E.

Here, restriction
the S**
is
N.
=
the

number of
told

fanticlai
 erp[pS(m,)-en
z: i

variable from 343 to

[n3
Chaying the causes a

restrickie
San
For Ferlinions, Mn 0
=
or 1

For Bosom, mi:0, 2...

For example, Nis

5(3)
[Se-(9(2)
q(z)
+
+

z =

'e PE"E(k)
=

Eri?
-
 The constraint, EM:N can be remand by

canon
considering
a

grand ensemble

2:Tr(e
-

P(1 -

ui))
for non-interading
is particle
For an
system, N
particle.
EePMN [
-

PE, Esas
2: -

N1
=
[ES

G
GPM
=

z
Wil

2 ePMr
=
E
2

[e- [*[(n)
N( = Emil

I
E
y
eBrie -

[(a)

Seanz. Paa e

(Eca) u)
2: Either
-
 hu
We can do thesummation independently
Such k,
7
([(n) n)
-Run
-

2:T5e
I wi

Far fu y +1,
=
M 0, 2...
7,)M2
=

=
0, 1,
(Busoe)
(Fermion)

(5(r) -

n)]

a)
-

I came
e

at

(scan-n)]
 P((x) n)]
h(I(1
-

e.ai e
+

([(n) m3)
-

-[r(1+
-

P(4()
n3)]
-

((((1
-

deat =
-
-

1999
n3)]
-

(1
-

= -
-
e

yep(91) -))
()-
1.2: +

2 Se-4(E-mine
=

P( -
n) en

P([n)) Ie
=

(in)=-1 en (2) atconstant M.

-(p()
 number (vi) a fixed ano
the
occupation
for

fac:
-

(-7 e91-ye.)]

-Seein -petethe BE

[ein)
_ whn z

number,
The average particle
()
=E(Y) ?"-
=

El

End-
 for non-relativegar
Equation of state

Quantum states also have

spin degeneracy.
in absence
this of
an external magnetic field,

(2 S+1)
the
degeneray g
:

Py =

Iny &Semi-classical approach?

=
-

48 fr)l- yesp[-+3)
Commuting sum to
an
integed,

Sato (91-920 P(*)3]

-

Ply: -

75

Similarly,
ii. 11:
I
-

ep
(I-1

it
is
tert-
 form
All these
equation contain a

pla
So we
simplify the
integration by banging the

.
B
"
variable, a =
k:

t
a n
knt 2
- ↳ =

e
dm:
it
qze 44y)
75/s[1-
-

44y
-

Since I
integralisspherically symmetric,
Jan => S4nhdm.
&By: 44."(-qze-*] X

R:
)"(1-18] -

side
e -
 as
the -

One can
interacte 8,
X

R:
Jair(1-1)
Intering by parts

↳(err (-get) -

)
listed
pay:

Sinclab, ay I
=

p4 0,)tes
=

We define a
function, for() itic.
=

Its
(m-!: fm *de, (t)!:,
r= P, et
understand
proceed faulton,
To we
need to

offor
the
propertion
I dete
↑
for:
antic!
am- z.)-yze)
0

i!!
well ofsmall z,

it
fa:antic?) my. yee* (-yzet

!Sam,14zee
-! *some- 0
du
 fo: iii, Same-du d

I:E y 2n,n y
=

X I
am dy: 2 de

-
-

I gmt. 1. dy
ram 2
-

f=z yz +ye (m!

+

am.
-

RM
the ideal limit. E=e
EC, in
gan
- z,a

Lays negation le is

For the relating

for
the
gas

n =
fain
is:fi z
=

yttt...
+

When EC, we
ignon
the
quadratic and the
higher order ferms,
myd- Z- (firstorder approximation).
I

For the
higher order.
m
I
z = -

For second order,

2 (*)
z =
-

Third ordn,

- (T-j-t(
=

O(*)"
+

A
=

+(- )()'+
0(2Y"
 Now, we know that,

pin: I I
S

Y
ppy.:
=+
1t t...
Incentthe value ofafrom the
premio, upt
O(63)"

- E)(t-sti) (**) +

((*))+st(*).
3

44
=45( (()+ (-5i)(7,..
-

=>
By:4'
-

x(*)+(t
-

5) (*)..
-
Vindelient.
Degenerate fan, E

quantum limit,
In the the differences between

Fermions and Borons become caucal, so

we frentboth there came

sequately.

billatthe
theopet
When [Me) -0, Ex
m, (M2) +
1
ECM, .

almost furt
AtT - 0, B -

00, <Ma) is a
step

met
E(M] l
=
called Re
is

Formenergy.

levels
E
All one-particle
with
when 3:
EF, every 2 Ein
occupied
For ideal 9(2):h
you -

2m,

ki be calculated,
The fermi wave number can

U,
A all the levels, below Itis occupied.

N:
grs* 8V
=

de
= I
a =

(h)", E( Eq

When I to, the Fermi sea modified,

is

To calculate that,

we have, fr:is its

-is: (mm! -) let u

fin-fule"ti)
de
 We take 2: 1z+h

x
0,
BM t 8
z e,
-
=

n
2, x t I
t
- -

0
l
- =

i 6,7 2
et:ex
~ - +

fir: it -

(n)
da

-Rate (anti) 22
it

Sat.
m

(2)
-

-
An t
I of(e).

fir=
estn nest
-
gatt"if (at)
D

the intral Set t

(it)= I et
Cetti)

-Setat for odd of4.

vanishes powers
(Since the intrant in

an odd fundion).
 For ever ①,

I(et):at" (it).

asan
e

set): afl

["!
fir: laast] attt (at)
2
20
=

fall.
fri=
HasSonis
m!
,
for even

e
Metis!
-

s
 hi lt(2.f()
fi= cm(m-1)
+

fi(i) (m)(m
+

#mE? [nz
·

Fl)
....
Sommerfield
= >

expension.
fill= I, fill):I:fil) - 7

fi fan=
2 12
-
((1+ mm2 mm.) +

number denh,
In degemats
the limits the

hat
Ice".]
-

=fy:
(3/2)!
-

213.

ene:(EE)!)" Iit ]
We
geta recursive relation
bar.
 In the lowestorder, at T-0,

215

Maz:pr= (flat)")
qr (y)*. he
=

m
(I also
=

M
(6) the
=
-
EF

-
at
For the order,
next
substitute =

BEI
-

21s

pu PE =

(+as)
Since
is samall, M-EF(1-, s,)
u
E! ()-...]
= -
 M

·
at T 0,= M EF
=

at T 0,
=
M -
+
0

Aus T
O
TETF

of
Mao, when, I in
is
order
the
E
for
apressure,

pp: f() -

[ ...)
(E)! E-1)! =
15
=
I

value
the ofRnz) calculated,

(nz):EF) -
()*--(
Sie
PP 8
=

5
(PE)
15
- (*.)[*]

"11+*().)
-
 PP:PP(H i*(i)*...).
PPF GBS)"Pr:EEE
=

Pr
= 3Er.1(PEr)"
=

I ↓S
e

-- ↓n(1 0) =

Pe
has finite
temperature
a

Fermi-gar atzero
Pr
Pr: 2 Esh.

·e
pressure, E

and
energy E.
E EP
= =

E IP(H*??...)
=

to
=nE)():..).
E:Eckst(1 *(I)*.]
TF:Fermi temperature,
-2

E:VE2kntr.I
ar: · 2T

Cr =IN
+OCE)

-......
inwee

T
Degenerate Bose Gas
-

ex(r)
occupancy (25):
- -

The
mean -
in)
-

~=
Etan,"Ezits-,
If state E:EC50)
the
ground 0,
=

= z,
z
diverge
1
No
+
as
-

alr, (45) 50 In

this condition in satisfied when I

In other word, S(4) -M40

M min (E(i))
of Emin:0.
In time care ideal
fan,
Mo
-
 I
be varies from 80 - r

rBar
vain foraa e
e
2
with in the internal o to Z.

us
the functions It has a finite value for

For MEl, f," divers

at2-1

One can show that

- (((z) Ifm-,(z).
=

the
N, are use

density
m:
To calculate the

meselect
I

ele:file.However,to afive t h e
(2n)5
zero wagt,
a
k
eudch
=

Similar, It:
Ida ,mxo,
for x =0

State adds zero

weight-
 So, fit provide only
the
density ofexcited
states, Mx

whole
now, which a
in large number

when zel

f 31.
(ititsit. ).
nx
2
=

atz 'Ya=m*=
I
15(3),
↓3
15(x) 2.612...
=

allowed the excited state.

itisinmaximum
deadly in

et.V n*;/h
=
maximum
mumble o particle in

the excited strate. bon*:f, If<nt

all

In general for any

zt (0,17, maximum
the

atthe excited stat n, -

85(3/).
occupancy

If u <nt, or
b>g(3k),
v(n-nt) particle
has be
to accommodeled tothe
state.
ground
 Stsk vs. 2 a

↑-------..(9) 2.612..

Ii..
=

3
nx
I

s
If be accommodeled
u
<E(sk), all the
particles can

excited
the
in
states.

ofparticles has to
25(1) the rest
Butwhen
state.
be accumulated
only
the
in ground

For ud be increased
by
a

given m, can increasing

I
↓ and
by decreasing the
temperature.
At the critical TC,
temperature,

-mist" E(%).
=
 213
im
(ie: (55) are

Whee TT, maximum Nt= 9Vg((()

53
the
to
Particle can be accommodated

ecided state.

The ofthe
rest particle
v-rt
v(n
=
-

55((()
particle will be att he ground state.

This is called Boe-Einstein condensalim

-

When Ito, TN,

N-rtwnv=v, all the particles are

slots.
condensed atthe
ground
When I <Tc M 0,= and in limity densely
n* g =

5(%) a +32
53

-nt

Fin
n

esure.
BP
yft.
= For + <Tc, 5 =
1,

P x8 3(5)
a
=
1.34
=

55
5/2
TT p- + also, P is idependentofdensely
This
-

implies infinite so
unpressibility
The internal energy:

=:
IPV 2V
=
battle at fi

Cr
)rw
:

eve
isis,

Athigh temperature, we can

expand powers ofz
in

(ItI: (