Major Concepts - ww2.chemistry.gatech.edurh143/courses/... · – Translations may satisfy ideal...
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 1
Major Concepts • Calculating observables using Statistical Mechanics • Noninteracting Systems
– Separable approximations – Transformations to separable Hamiltonians – Harmonic Oscillator – Ideal Gas – Other examples?
• Statistical Mechanics of Gases – Classical Mechanical Systems
• The Kinetic Energy is �Separable� • Molecules
– Translations may satisfy ideal gas condition – Rotations and vibrations are nearly separable
• In non-interacting limit, recover ideal gas law – In general, must use numerics or approximate theories…
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 2
Noninteracting Systems • Separable Approximation
• Note: lnQ is extensive! • Thus noninteracting (ideal) systems are reduced to
the calculation of one-particle systems! • Strategy: Given any system, use CT�s to construct
a non-interacting representation! – Warning: Integrable Hamitonians may not be separable
€
if Η(qa ,qb , pa , pb ) =Η(qa , pa) +Η(qb , pb)⇒Q =QaQb
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 3
Harmonic Oscillator, I In 1-dimension, the H-O potential:
€
V = 12 kx 2
€
H = T +V =p2
2m+12kx 2 = E
€
Q =12π!#
$ %
&
' ( dx∫ dp e−βH (x,p )∫ =
12π!#
$ %
&
' ( e
−β2kx 2
∫ dx e−β p 2
2m∫ dp
€
V = 12 kx2
The Hamiltonian:
The Canonical partition function:
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 4
Harmonic Oscillator, II
€
Q =12π!#
$ %
&
' ( e
−β2kx 2
∫ dx e−β p 2
2m∫ dp
€
Q =12π!#
$ %
&
' (
2πβk
#
$ %
&
' (
2πmβ
#
$ %
&
' ( =
m!2β 2k
€
ω ≡km
€
⇒Q =1!βω
€
e−ax2
−∞
∞
∫ dx =πa
The Canonical partition function:
After the Gaussian integrals:
Where:
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 5
Harmonic Oscillator, III
€
Q =12π!#
$ %
&
' ( e
−β2kx 2
∫ dx e−β p 2
2m∫ dp
€
⇒Q =1!βω
The Canonical partition function:
But transforming to action-angle variables…
€
Q =12π!
#
$ %
&
' ( dθ
0
2π
∫ e−βωI
0
∞
∫ dI
=12π!
#
$ %
&
' ( ×2π ×
1βω
#
$ %
&
' (
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 6
Quantum Harmonic Oscillator
€
Q = e−βEnn=0
∞
∑
En = !ω n +12
'
( )
*
+ ,
⇒ Q = 2sinh(!βω / 2)( )−1
≈1!βω
as !→ 0
The Canonical partition function:
Which can be readily summed to…
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 8
Classical Partition Function • Note that we have a factor of Planck�s Constant, h,
in our classical partition functions:
• The origin of the prefactors are: – h ensures that Q is dimensionless – N! accounts for indistinguishable particles – In the special case of the HP partition function, it
recovers the classical limit correctly • More generally, Q remains correct even with
interactions between multipled dof�s!
€
Q =1N!
12π!#
$ %
&
' (
N
dxN∫ dpN e−βH (xN ,pN )∫
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 9
Observables in HO
€
Q =1!βω
€
E = −∂ ln(Q)∂β
=∂∂β
ln !βω( )( ) =1β
= kBT
€
e−ax2
−∞
∞
∫ dx =πa
The Harmonic Oscillator (HO) canonical partition function:
Recall
€
V = 12 kx2
€
K.E. = 12 kBT
EquipartionTheorem
" # $
€
V = 12 kBT
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 10
Gas Consider N particles in volume, V
€
V (! r 1,...,! r N ) = Vij
! r i −! r j( )
i< j∑
€
Q =12π!#
$ %
&
' ( 3N
d" r ∫ d" p ∫ e−βH
" r ," p ( )
with a generic two-body potential:
The Canonical partition function:
€
d! r = dr1dr2...drN
€
T( ! p 1,...,! p N ) =
! p i2
2mii∑
and kinetic energy:
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 11
Integrating the K.E. Q in a Gas
€
Q =12π!#
$ %
&
' ( 3N
d" p ∫ e−β
pi2
2mii
N
∑d" r ∫ e−βV
" r ( )
€
Q =12π!#
$ %
&
' ( 3N 2miπ
β
#
$ %
&
' (
i
N
∏32
d" r ∫ e−βV" r ( )
May generally be written as: (Warning: this is not separability!)
€
Q =12π!#
$ %
&
' ( 3N
d" r ∫ d" p ∫ e−βH
" r ," p ( )
€
e−ax2
−∞
∞
∫ dx =πa
With the generic solution for any system
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 12
Interacting→Ideal Gas Assume:
1. Ideal Gas → V(r)=0 2. Only one molecule type: mi=m
€
Q =12π!#
$ %
&
' ( 3N 2mπ
β
#
$ %
&
' (
3N2
V N
€
d! r ∫ e−βV! r ( ) = d! r ∫ = V N
€
2miπβ
$
% &
'
( )
i
N
∏32
=2mπβ
$
% &
'
( )
3N2
The ideal gas partition function:
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 13
The Ideal Gas Law
€
Q =12π!#
$ %
&
' ( 3N 2mπ
β
#
$ %
&
' (
3N2
V N
€
P = −∂A∂V$
% &
'
( ) T ,N
€
dA = −SdT − PdV + µdN
€
A = −kBT ln Q( )
€
P = kBT∂ ln(Q)∂V
€
P = kBTNV Ideal Gas Law!
Recall:
The Pressure
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 14
Ideal Gas: Other Observables The image cannot be displayed. Your computer may not have enough memory to open the image, or the image may have been corrupted. Restart your computer, and then open the file again. If the red x still appears, you may have to delete the image and then insert it again.
€
E(T ,V ,N) = −∂ lnQ∂β
A(T ,V ,N) = −kT lnQ
S(T ,V ,N) =E − AT
Recall : A = E −TS
€
Δ(T ,P,N) = e−βPVQ(T ,V ,N)dV
0
∞
∫G(T , p,N) = −kT lnΔ
S(T , p,N) = k lnΔ + kT∂ lnΔ∂T
(
) *
+
, - N,P
€
Q =12π!#
$ %
&
' ( 3N 2mπ
β
#
$ %
&
' (
3N2
V N
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6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 15
Noninterating Two-Level Systems • Examples:
– Photon Gas – Phonon Gas – Magnetic Spins
• In all cases the Hamiltonian looks something like
• We’ll obtain the ideal Q next time.
€
Η(H ,N) = −niµH
i=1
N
∑
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Completing the Square
6755 Lecture #8 —Rigoberto Hernandez
Ideal Systems 16
(x� a)2 + (b� x)2 =�x2 � 2ax + a2
⇥+
�b2 � 2bx + x2
⇥
= 2x2 � 2(a + b)x + a2 + b2
= 2�x2 � (a + b)x
⇥+ a2 + b2
= 2⇤
x2 � (a + b)x +(a + b)2
4
⌅� (a + b)2
2+ a2 + b2
= 2⇤
x� (a + b)2
⌅2
� 12
�a2 + 2ab + b2
⇥+ a2 + b2
= 2⇤
x� (a + b)2
⌅2
+12
�a2 � 2ab + b2
⇥
= 2⇤
x� (a + b)2
⌅2
+12
(a� b)2
� +⇥
�⇥dx e�2(x� (a+b)
2 )2� 12 (a�b)2 = e�
12 (a�b)2
� +⇥
�⇥dx e�2x2
� +⇥
�⇥dx e�(x�a)2�(b�x)2 = e�
12 (a�b)2
⇥�
2