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Lecture 3-1 : Introduction to statistical mechanics

In this lecture ,
we introduce the 3rd law of thermodynamics ,

which postulates one additional property of

Entropy .
We discuss how
this law relates £ the of Entropy
microscopic After
definition .

that ,
we move on to an introduction of the field of statistical
mechanics ,
the microscopic counterpart of thermodynamics .

Core concepts covered in this lecture material

◦
The 3rd Law andits relationship to absolute zero
Microscopic Definition of Entropy
◦

• Microstates statistics and macroscopic

averages

The Third law of Thermodynamics

The 3rd law postulates that there is an absolute minimum value of entropy ,

5=0 that occurs at the lowest possible temperature ,

F- 0 .

stated more
precisely ,

S→0 as 1-→ 0

This state referred to Absola£Zn"_

"

5=0 , to is as

We rationalize the 3rd law manifestation at the

can as a
microscopic
definition of Entropy

5. =
kosher
J TNumber
Boltzmann
-

of available
Constant microstates

Thus
s=0im[sR=1_only
,

at Tao one micro state

,

is available !
 2- 31

We now introduce the topic of statistical mechanics, which , represents

the microscopic counterpart of thermodynamics
scientific framework, . As a

statistical mechanics allows us £ rationalize the observable properties of

physical systems in terms of the statistical prop hrs of its microscopic -

constituents Statistical mechanics is exciting hearse it meals the microscopic

.

origins
of many opaque concepts (such as heat, temperature , and entropy ) .

The G-nndntions of statistical mechanics are summarized

by
a macroscopic observable into its microstates contributions .

Specifically ,
consider a quantity A which ,
is an observable
state of
property of the macro
system a .

②
⑦ N " ③ ʳ ④ a ⑤ ⑥
Abs =
¥e
5- A ;
=
tw E- Wr Ar =¥ErAr=IPvAr
ww
=
(A)
the
sequence
of a snmoÑ number at times
states sampled during all
unique micws-h.LV appeared
our observation microstates
during observation

Aobs This is the value of A that we observe .

IN ¥ A. represents
Our macroscopic observation
②
an
average over a
,
a
large number (a) of microstates
,
very .

~ Here, we have reorganized the sum over

the observed
③ IN Wr Av Set of microstates
The
into
specifies
a sum

the # of
over all possible microstates
micro state
quantity Nv times each was

sampled during the observation .

Here make the assumption that NHN equivalent

④ is
we
sr

F- BAR
to the
equilibrium probability to observe micro state V which
⑤
,

we denote as Pv

⑥ (A) Here , we define <×> as the equilibrium average f-

quantity X .

This progression important because it sets out the central

is

hypothesis for statistical mechanics that the macroscopic properties ,

of a system can be represented as weighted ( by Pv ) average over a

micros tut properties ( i. e. ① → SO)

?⃝
 3- 3-1

This progression also establishes an

important concept: That we can

associate an equilibrium probability ,

Pr , £ individual microstates in

the system .

wereeg.ua/ly1itu1g,i.e.,Pr--constant--'/R!WJ
In have done this
fact, we previously when we assumed

that for systems at fixed (d) V

,
N) that all microstates

The first step in statistical mechanics is to

figure out how to determine
the microstates probability ,
% .
(if we know Pu h - all of the microstates,
then we can
comport average system properties !) .
This can be

challenging because the

,
value of Pr depends on the conditions of
the system We .
can make some generalizations though starting ,

from the postulate ,

The Micro canonical

distribution law specifies the

\p%%Tʰ
's

relative probability of observing any

particular microstates from amongst
all possible microstates when
for systems at
a

fixed ↳ V
,
N system has fixed U,
V and N
,
.

More Precisely ,

=§yv,n
if did Viv and Near
Pr
, ,

0
,
otherwise

where RLU, V, N) = total # of microstates with U,

V N
,
.
This definition is

useful because it includes the possibility of microstates with Uv ,

Vr, o- Nv

that are not

equal t U
,
V
,
o-
N .
These states exist
, they are
just
this
not members of particular ensemble .