The Boltzmann Distribution 2013

Ludwig Boltzmann (1844 1906). His tombstone bears the insri!tion

S " k#logW
Association
$he intensit% o& a transition &rom one 'uantum state to another
resulting &rom the interation o& eletromagneti radiation with a
moleule is not onl% de!endent on(
mathing the energ% o& the radiation with di&&erenes in
moleular energ% le)els and
seletion rules go)erning allowed transitions* but is also
de!endent on
the number of molecules populating the initial state in the
transition.
The Boltzmann distribution tells us how the internal energ%+ U o& a
s%stem is distributed amongst the )arious energ% le)els o& the s%stem.
Internal energy+ U+ is the total energy o& a s%stem (the matter we are
stud%ing).
$here are two &undamental !arts o& the internal energ%( the inetic
energy and the potential energy. ,or hemial s%stems+ the -ineti
energ% is due to the random motion o& the !artiles that ma-e u! the
s%stem.
Boltzmann.0. 1
$he !otential energ% is the energy stored in bonds and in the
electronic and nuclear states of the atoms that ma-e u! the matter.
$he -ineti energies would be translational (mo)ing the !artiles
&rom !oint to !oint)+ !ibrational (strething and shortening the bonds
li-e tin% s!rings)+ and rotational (s!inning the !artiles li-e tin%
to!s).
$he !otential energ% would be all the energies due to all o& the bonds
and all o& the eletrons/ 'uantum mehanial energ% states+ some in
the ground and some in )arious e0ited states. $he )arious di&&erent
om!onents o& the internal energ% &or the )arious di&&erent !artiles in
the s%stem are onstantl% hanging+ as !artiles ollide and as
eletrons hange 'uantum states. Beause it is so om!liated+ the
internal energ% annot be alulated+ e)en &or the sim!lest o& hemial
s%stems. Howe)er+ when a hemial hange ta-es !lae+ internal
energ% is trans&erred to or &rom the s%stem. 1e an obser)e and
measure the internal energ% hange+ 23 (4 is the other s%mbol &or
internal energ% seen in some hemistr% and most !h%sis te0ts).
5ur s%stem is 'uantised with energy le!els
i
where i is an inde0
whih an be used to label the le)els. $he nature o& the le)els is
irrele)ant. $he lowest le)el will be labelled with the inde0 i "0+ so that
i 6 1 0
... < < <
7i)ing that our moleules are in a state o& onstant thermal agitation
it is e)ident that a gi)en moleule will not alwa%s be &ound in the
same state. 8t is true+ howe)er+ that o)er a !eriod o& time there tends to
be the same number o& moleules in a gi)en state. 8& we label the
number of molecules in state i as n+ then the total internal energ% o&
the s%stem is
Boltzmann.0. 6

= + + =
i
n n n n U
i i 6 6 1 1 0 0
...
1.
$he ratio o& moleules at the 9
th
le)el to the others at di&&erent le)els
shows an e0!onential )ariation. $o gi)e this ratio we use the
Boltzmann distribution law(
( )
( )

=
i
i
9
: ; e0!
: e0!
kT
kT
N
n
j
6.

=
i
i
n N
where N is the total number o& moleules !o!ulated all the !ossible
le)els+ k is the Boltzmann onstant+ and T is the tem!erature in <el)in.
$urning to t"o le!els one o& them is !o!ulated b% n
1
the other b% n
2

moleules+ and N " n
1
= n
2
.
( )
( ) ( ) kT kT
kT
n n
n
: e0! : e0!
: e0!
6 1
6
6 1
6
+

=
+
and a&ter sim!li&iation
( ) ( )
( )
( )
( )
1
: e0!
: e0!
: e0!
: e0! : e0!
1
6
1
6
6 1
6
1
6
6 1
+

+
= + =
+
kT
kT
kT
kT kT
n
n
n
n n
and its rei!roal gi)es the n
6
:n
1
.ratio
( ) ( ) ( ) kT kT
n
n
: e0! : e0!
1 6
1
6
= =
where 2 "
6
;
1
is the energ% di&&erene between le)els.
8n general+ the Boltzmann distribution tells us that the ratio o&
!o!ulations )aries e0!onentiall% with the energ% di&&erene+ )iz.(

=
kT

n
n
j
i
9 i
e0!
..
Boltzmann.0. .
$he dynamic modes into whih the internal energ% an be distributed
are( translation#$ rotation#$ !ibration# and electron#energy.
$a-ing the natural logarithm o& 3'. .
kT

n
n
j
i
9 i
ln

=
4.
$he natural logarithm o& the ratio o& the number o& !artiles in two
di&&erent energ% states is !ro!ortional to the negati)e o& their energ%
se!aration.
1e shall now wor- out population ratios &or di&&erent -inds o&
energ% mode at room tem!erature+ 6>
o
? (698.1> <). 1e alulate
!o!ulation distributions &or one mole. $he denominator o& e0!onent in
3'. 4 ta-es the )alue
R=N
@
k " 8..14 A<
;1
mol
;1
+ and N
@
" 6.066 10
6.
mol
;1
RT " 698.1>#8..14 " 64B89 Amol
;1

RT " 6.48 -Amol
;1
(rounding).
%lectronic le!el population density ratio
,or an eletroni le)el di&&erene 2 is 'uite high. 8& we ta-e a
h%drogen atom in gas !hase 2 " 1000 -Amol
;1
. $he !o!ulation
o& the 6s e0ited state n
6s
relati)e to ground state+ n
1s
is
1B> 40.
1
6
10
48 . 6
1000
e0!

= =

= e
n
n
s
s
+ so the number 6s H;atoms at room
tem!erature is
40.
1 6

= e n n
s s
so that we an be )er% on&ident that there are no 2s hydrogen atoms
around at room tem!erature.
Boltzmann.0. 4
&ibrational le!el population density ratio
Ce0t we onsider )ibrational modes. 8& we ta-e ?5 moleules+ the
)ibrational 'uantum le)els ha)e an energ% se!aration o& around "6>
-Amol
;1
. Dibrational energ% le)els (v " 1+ 6+ .E) are muh more
losel% s!aed than eletroni ones. Hene
> 10
0 )
1 )
10 >
48 . 6
6>
e0!

=
=
= =

= e
n
n
8& we ha)e a s%stem ontaining 60000 moleules+ than
1 10 > 60000
>
1 )
= =

=
n
8t means that one out o& e)er% 60000 moleules is &ound at the &irst
)ibration e0ited state in a time a)erage.
'otational le!el population density ratio
Fotational le)els are muh more losel% s!aed than )ibrational
le)els. ,or ?5 the rotational energ% le)els are around 0.0> -Amol
;
1
a!art. 1e an write
94 . 6 .
48 . 6
0> . 0
e0! .
06 . 0
0 A
1 A
= =

=

=
=
e
n
n
$he &ator o& . in the e'uation abo)e re'uires some e0!lanation. 8t
arises beause the &irst e0ited rotational le)el A"1 is atuall% three&old
degenerate (i.e. there are . le)els all with the same energ%). $his
degeneracy &ator must be ta-en into aount when assessing the
!robabilit% o& &inding a moleule in a gi)en le)el.
Temperature dependence of population.
@ om!arison o& !o!ulation densities between temperatures 2( and
1000
o
).
?alulate the ratio o& moleules in e0ited rotation+ )ibration and
eletroni energ% le)el to that in the lowest energ% le)el.
Gata( T
1
" 6>
o
?+ T
6
" 1000
o
?
&irst e0ited energ% le)els are at .0 m
;1
rotation+
Boltzmann.0. >
1000 m
;1
)ibration+
40 000 m
;1
eletroni+
abo)e the lowest one.
@ssume that+ J " 4 &or e0ited rotation le)el+ and suh a le)el is 6J=1
&old degenerate.
Dibration and eletroni states ha)e no degeneraies.
Hlan- onstant h " 6.666 10
;.4
A:s+ )eloit% o& light c " . 10
10
m:s+
Boltzmann onstant k " 1..8 10
;6.
A:<+ $
1
" 698 <+ $
6
" 16B. <
'otation

I
= = = c h
c
h h
where

I
is the wa)enumber gi)en in m
;1
.
at T
1
( )
( )
8 . B
I
e0! 9
lower
u!!er
1
=

=
kT
hc
n
n

and at T
6
( )
( )
B . 8
I
e0!
lower
u!!er
6
=

=
kT
hc
n
n
8n eah set o& ten moleules at T
6
" 1000
o
? onl% one is at the lowest
energ% le)el.
How ha)e we got thereJ
Let n
u!
= n
lo
" 10 and &rom alulation n
u!
:n
lo
" 8.B+ ombining these
two
8.BKn
lo
= n
lo
" 10+ n
lo
" 10:9.B " 1+0.1 rounding n
lo
" 1
&ibration
@t T
1
( )
( )
008 . 0
I
e0!
lower
u!!er
1
=

=
kT
hc
n
n

and atT
6
Boltzmann.0. 6
( )
( )
.6. . 0
I
e0!
lower
u!!er
6
=

=
kT
hc
n
n
@ 40;&old inrement in !o!ulation in)ersion is aused b% the inrease
in tem!erature.
%lectronic
@t T
1
(
( )
( )
84
1
10 64 . 1
I
e0!
lower
u!!er

=

=
kT
hc
n
n

and at T
6

( )
( )
60
6
10 .4 . 6
I
e0!
lower
u!!er

=

=
kT
hc
n
n
Hratiall%+ all the moleules are in ground eletroni state at room
tem!erature.
$able &or summar%( tem!erature de!endene
en. le)els le)el di&&.
in m
;1
le)el di&&.
in -A:mol
!o!. densit% ratio
at T
1
" 6>
o
? at T
6
" 1000
o
?
eletroni 40000 4B9 1.64 10
;84
6..4 10
;60
)ibrational 1000 16 0.008 0..6.
rotational .0 0..6 B.8 8.B
Boltzmann.0. B
*olecules as Balls %nergy +e!els as Bo,es
Lu!!ose we ha)e 7 atoms (or moleules) and we introdue 'uantum
mehanis into the !iture+ that is+ the energies o& these atoms are
'uantized.
,or sim!liit%+ we will assume that the allowed energ% le)els are 0e+
1e, 6e, .e, 4e, >e, 6e, Be. $he )alue o& 0e is hosen as a re&erene
state+ 0e M 0 and measure all other energies relati)e to it.
1e an thin- o& these energ% le)els as bo0es. 1e ha)e 8 bo0es(
n
0
+ n
1
+ n
6
+ n
.
+ n
4
+ n
>
+ n
6
+ n
7
" B
$he e'uation abo)e shows that onl% B atoms ma% be &ound in the 8
bo0es.
$he total energy o& the s%stem is+ howe)er+ restrited. 8t should
alwa%s be e'ual -e. 8t means U " onstant.
$hus+
0e*n
0
+1e*n
1
+ 2e*n
2
+ e*n

+ !e*n
!
+ "e*n
"
+ #e*n
#
+ 7e*n
7
= 7e
3'. gi)es the total energ% re'uirement.
,or e0am!le( let/s sa% we ha)e > moleules with no energ%+ one with
.e and one with 4e. 8n details(
n
0
" > >K0e " 0
n
1
" 0
n
6
" 0
n
.
" 1 1K.e " .e
n
4
" 1 1K4e " 4e
n
>
" 0
n
6
" 0
n
B
" 0
Boltzmann.0. 8
8n the eight bo0es we distributed B moleules with s%stem/s energ%
e'uals Be.
$he maroso!i state o& the s%stem is de&ined b% a distribution on the
microstates that are aessible to a s%stem in the ourse o& its thermal
&lutuations. $he number o& mirostates in a marostate is alled the
multiplicity o& the mirostate.
$he number of microstates+ W is gi)en b% the &ollowing e'uation(
N... N N
N
6 1 0
n n n
N
W =
6.
and n
i
is the number o& atoms &ound in a ertain bo0. Go not &orget 0N
is one.
Table &or the !ossible arrangements o& B atoms and 8 allowed energ%
le)els(
?ase n
0
n
1
n
6
n
.
n
4
n
>
n
6
n
B
W
1 6 1 B
6 > 1 1 46
. > 1 1 46
4 > 1 1 46
> 4 6 1 10>
6 4 1 1 1 610
B 4 1 6 10>
Boltzmann.0. 9
8 4 6 1 10>
9 . . 1 140
10 3 2 1 1 .20
11 . 1 . 140
16 6 4 1 10>
1. 6 . 6 610
14 1 > 1 46
1> B 1
,or ase one(
n
0
" 6
n
1
" 0
n
6
" 0
n
.
" 0
n
4
" 0
n
>
" 0
n
6
" 0
n
B
" 1
N " B
B
B60
>040
N 6 N 0 N 0 N 0 N 0 N 0 N 0 N 1
N B
= =

= W
(6N"B60)
and &or ase 10+ similarl%+ omitting zero &atorials
460
16
>040
N . N 6 N 1 N 1
N B
= =

= W
Boltzmann suggested that i& one an obser)e suh an assembl% o)er a
long !eriod o& time+ each microstate "ill occur "ith e/ual
probability and one will &ind that the number o& ourrenes &or an%
!artiular set o& distribution is !ro!ortional to the number o&
mirostates that orres!ond to that set.
,or e0am!le+ in the abo)e s%stem+ there are a total o& 1-10 "ays or
microstates. ($he sum o& olumn W). $he !robabilit% o& ase 1
ourring+ &or e0am!le+ is B in 1B16. $he !robabilit% o& ase 6
ha!!ening is 46 in 1B16. $he !robabilit% that ase 10 is 460 in 1B16
(the highest o& all).
Boltzmann.0. 10
Ouantized eletroni ($) and )ibrational ()) states.
Additi!e material
*acrostates and microstates
$he state o& a s%stem is haraterized b% the )alues o& all the )ariables needed to om!ute the
!ro!erties o& the s%stem at a later time. 8& we use Cewtonian mehanis+ the state o& the
s%stem is haraterized b% the !ositions and )eloities o& all the !artiles in the s%stem. 8n
thermod%namis+ we use the e0!ression microstate to re&er to suh a state. $he !re&i0 miro
stresses the &at that we -now the !ositions and )eloities o& all the miroso!i om!onents
o& the s%stem. B% ontrast+ we use the e0!ression macrostate when we onl% s!ei&% the
)alues o& the maroso!i !arameters o& the s%stem+ li-e !ressure+ tem!erature and so on. 5&
ourse+ this does not haraterize the s%stem om!letel%. $here ma% be man% !ossible
mirostates that are onsistent with a gi)en marostate. $he number o& mirostates in a
marostate is alled the multiplicity o& the mirostate.
Boltzmann.0. 11