物理化學(三)

Physical Chemistry (III)

應用化學系
朱超原 副教授
Text book: Physical Chemistry 3rd edition, Mortimer, 2008

Reference books:
Physical Chemistry 2nd edition, Engel and Reid, Pearson 2010
Physical Chemistry, McQuarrie and Simon, 1997
Atkins' Physical Chemistry 7th edition, Atkins and Paula, 2002

Homework：25%
Midterm： 35%
Final： 40%

物理化學(三) 應用化學系朱超原老師 2
Physical Chemistry I (PChemI) Many molecules in box

●●●●●
●●●●●
●●●●● State of Equation
P
PV  nRT 2
T2
Ideal gas equation

 2 
P  an  V  nb   nRT
T1  2 
 V 
V Van Der Waals equation
T 2  T1 Why is V2, not V3
物理化學(三) 應用化學系朱超原老師 3
Physical Chemistry II (PChemII) One molecule in box

Schrödinger equation

Hˆ  k  E k  k
Temperature

Energy is discrete

time Pure
quantum
Infinite molecules Classical  Quantum

One molecule
物理化學(三) 應用化學系朱超原老師 4
Physical Chemistry III (PChemIII)
From one to infinite molecules
●●●●●
● ●●●●●
●●●●●

 2 
Hˆ  k  E k  k P  an  V  nb   nRT
 2 
 V 

 Ek 
Partition function Q   exp   
k  k BT 

物理化學(三) 應用化學系朱超原老師 5
I. Molecular energy levels for
macroscopic thermodynamics

• Introduction
• Quantum statistic mechanics
• Simple translational, rotational, and
vibrational models
• Partition function
 I-1. Introduction
Four identical diatomic molecules in box

V N 4 E  Nhv

Assume only vibrations (no translation and rotation)

E  hv n1  n 2  n 3  n 4   2 hv 

n i  0 ,1,  Zero-point energy

(constant)
Use k  n1 n 2 n 3 n 4 
物理化學(三) 應用化學系朱超原老師 7
E  4 hv

物理化學(三) 應用化學系朱超原老師 8
 state No. k  n1 n2 n3 n4 N0 N1 N2 N3 N4 W N 
1 1 1 1 1 0 4 0 0 0 1
2 0 1 1 2 1 2 1 0 0 12
3 0 1 2 1 1 2 1 0 0
4 0 2 1 1 1 2 1 0 0
13 1 1 2 0 1 2 1 0 0
14 0 0 2 2 2 0 0 0 0 6
15 0 2 0 2 2 0 0 0 0
19 2 2 0 0 2 0 0 0 0
20 0 0 1 3 2 1 0 1 0 12
21 0 0 3 1 2 1 0 1 0
30 1 3 0 0 2 1 0 1 0
31 3 1 0 0 2 1 0 1 0
32 0 0 0 4 0 0 0 0 1 4
35 4 0 0 0 0 0 0 0 1
Distribution Distribution No. of
E  4 hv Micro-state Micro-state Distribution
35 mol states n 1 n 2 n 3 n 4  n
物理化學(三) 應用化學系朱超原老師 9
The probability distribution of molecular states: E  4hv  35

No. probability
n1=0 15 p 0  15 / 35  0 . 42875
n1=1 10 p 1  10 / 35  0 . 28571
n1=2 6 p 2  6 / 35  0 . 17143
n1=3 3 p 3  3 / 35  0 . 08751
n1=4 1 p 4  1 / 35  0 . 02857
4
 pn  1 normalization
n0

4 4
E
Average energy    pn n   pn nhv  hv 
n0 n0 4

物理化學(三) 應用化學系朱超原老師 10
The most probable distribution of molecular states :

n1=0 n1=1 n1=2 n1=3 n1=4

12 3 6 3 0 0
W N 
12 6 3 0 3 0
9 9 3 3 0

Most probable probability

p 0  9 / 24  0 . 3750
p 1  9 / 24  0 . 3750
p 2  3 / 24  0 . 1250
p 3  3 / 24  0 . 1250
p 4  0 / 24  0

物理化學(三) 應用化學系朱超原老師 11
Boltzmann distribution of molecular states :
 nhv    nhv  1
pn  exp     exp   k T  
 kBT  n0  B  1 exp   hv 
 
 kBT 
Normalization constant
 
 hv    nhv 
pn  1  exp     exp     pn  1
  k BT   k BT  n0
  hv E  N  4
   pn n   pn nhv    hv
n 0 n 0  hv  4
exp   1
 k BT 
 hv   hv 
exp    1  1 exp    2
 k BT   k BT 
物理化學(三) 應用化學系朱超原老師 12
 Boltzmann distribution Exact distribution
  hv   nhv  1 n
pn  1  exp   exp    2
  k B T   k BT  2
p 0  0 .5
p 1  0 . 25 p 0  15 / 35  0 . 42875
p 2  0 . 125 p 1  10 / 35  0 . 28571
p 3  0 . 0625 p 2  6 / 35  0 . 17143
p 4  0 . 03125 p 3  3 / 35  0 . 08751
p 5  0 . 01562 p 4  1 / 35  0 . 02857
p 6  0 . 00781 p5  0
 p6  0

When N →∞, two distributions are equal

page1046: problems 25.1(N=3 ) “not homework”

物理化學(三) 應用化學系朱超原老師 13
 I-2. Quantum statistical mechanics
N identical molecules in box (V)

1 2 3 ●●● N

No interaction between two molecules

Hamiltonian

Hˆ tot  Hˆ 1  Hˆ 2   Hˆ 3     Hˆ  N 

Hˆ 1  k 1    k k 1 

物理化學(三) 應用化學系朱超原老師 14
Boltzmann statistical mechanics

 1, 2 ,3,  , N    k1 1 k 2 2  k 3 3   kN N 

Fermi-Dirac statistical mechanics

 1,2,3,  , N     1  k1 1 k 2 2  k 3 3 kN N 

1 P
N ! P 123N 
Antisymmetry
Bose-Einstein statistical mechanics

 1,2,3,  , N    k1 1 k 2 2  k 3 3 kN N 

1

N ! P 123N 
Symmetry

物理化學(三) 應用化學系朱超原老師 15
Temperature Energy
vacuum

T=? ● OK to define

●●

T Ok to define N particles

How big is big enough to define

temperature ?
物理化學(三) 應用化學系朱超原老師 16
Energy in an atom or molecule
Connecting macroscopic thermodynamics to a molecular understanding
requires that we understand how energy is distributed in a molecular scale.

ATOMS: The electrons: Electronic energy. Increase the energy of one

(or more) electrons in the atom.

Nuclear motion: Translational energy. The atom can moves

around in space.
MOLECULES:
The electrons: Electronic energy. Increase the energy of one (or more)
electrons in the molecule.

Nuclear motion:
Translational energy. The entire molecule can translate in space.
Rotational energy. The entire molecule can rotate in space.
Vibrational energy. The nuclei can move relative to one another.
物理化學(三) 應用化學系朱超原老師 17
Further separation of equation motions for a single molecule:

Hˆ 1  k 1    k k 1 

Eigen-Wavefunction

 k 1   ktrans 1 krot 1 kvib 1 kelec 1

Nuclear motion Electronic motion

Born-Oppenheimer approximation
Eigen-Energy

 k   ktrans   krot   kvib   kelec

物理化學(三) 應用化學系朱超原老師 18
Energy and time scale

Tape of Δt=h/ΔE
Type ΔE (eV)
radiation (s)
Translation 10-18 4000

Rotation 5*10-4 Microwave 10-10

Vibration 0.3 Infrared 10-14

Electronic 5 Visible/UV 10-15(fs)

Energy gap increase Motion getting fast

物理化學(三) 應用化學系朱超原老師 19
(1) Almost all molecules are in the electronic ground state.

(2) Many molecules are in the vibrational ground state.

(3) Almost all molecules are in many excited rotational states.

(4) Almost all molecules are in many excited translational states.

So, translational states are most probable.

物理化學(三) 應用化學系朱超原老師 20
 I-3. Simple translational, rotational,
and vibrational models
 
Translational energy levels
 2 d 2

V ( x)
 2
 E   x ,  0    a   0
2 m dx
x a
 n 
2 0
1  n 
 n x  
2
n    sin  x , n  1,2,3
2m  a  a  a 
In 1D, there is no degeneracy , gn = 1
In 3D

h  n x2 
2 2 2
n y n 
 nxn ynz    z
8m  a 2
b 2
c 2 
 
n x , n y , n z  1, 2 ,3 , 
物理化學(三) 應用化學系朱超原老師 21
 a  b  c
( nx , n y , nz ) probability

p 321  6 exp   321 / k B T 

nx2 +n y2 +nz2

p221  3 exp   221 / k B T 

p111  exp  111 / k BT 

物理化學(三) 應用化學系朱超原老師 22
 Rotational energy levels:
Moment of inertia
I  m1 R12  m2 R22   Re2
R2 Re
m2 R1
2
KY JM  ,    J J  1Y JM  ,  
2I m1
Energy levels Center of mass

2
J  J  J  1, J  0,1,2, 
2I
probability
Degeneracy pJ   2J 1 exp   J /  kBT  
g J  2J 1

物理化學(三) 應用化學系朱超原老師 23
Vibrational energy levels:

The quantum harmonic oscillator model (diatomics)

Model the vibrational m1 k m2
k
motion as a harmonic 
oscillator, two masses 
attached by a spring
m m 2
  1
m 1  m 2
 d n (x) 1 2
2 2
  kx n (x)  Enn x
2 dx 2
2 probability
 1
 n    n 


2
n  0,1, 2,  p n  exp  n / k B T 

•Equal spacing
•Zero-point energy (even at absolute zero temperature)
物理化學(三) 應用化學系朱超原老師 24
Dissociation energy

1
De D 0  

J
2

-19
De

V(l )/10
D0

n=0
For hydrogen molecule
Dissociation energy
De = 458 KJ/mol
D0 = 435 KJ/mol
R/pm

物理化學(三) 應用化學系朱超原老師 25
 Degrees of freedom

To specify the position of a molecule with n nuclei in space we

require 3n coordinates, this is 3 Cartesian coordinates for each
nucleus. We say that there are 3n degrees of freedom.
degrees of freedom
(3n total)
Translation:
Motion of the center of mass 3

Rotation:
Linear molecule 2
Nonlinear molecule 3

Vibration:
Linear molecule 3n-5
Nonlinear molecule 3n-6
物理化學(三) 應用化學系朱超原老師 26
(rigid) Polyatomic rotations pJ  gJ exp   J /  kBT  
pJK  2  2J 1 exp   JK /  kBT  
Linear molecules: 2
J  J  J  1, J  0,1, 2,  , g J  2 J  1
2I
Nonlinear molecules:
spherical top (baseball, CH4 ): I A  I B  I C
2
J  J  J  1, J  0,1,2,  , g J  2 J  1 2
2I
symmetric top:
J J 12 K 22  1 1 
Prolate  JK     , I B  IC  I A
2I B 2  I A IB 
g JK  22J 1
J J 1 K 
2 2 2
1 1
Oblate  JK      IC  I A  I B
2I B 2  IC I B 

asymmetric top (H2O): I A  I B  IC

All 3 moments of inertial are NOT equal.
物理化學(三) 應用化學系朱超原老師 27
Polyatomic vibrations: normal modes
For polyatomic molecules we can consider each of the nvib
vibrational degrees of freedom as independent harmonic oscillators.
We refer to the characteristic independent vibrational motions as
normal modes.
For example, water has3 normal modes:
Since the normal modes 3n-3 = 3
are independent, the
total energy is just the
sum: 1595 cm-1

 1
nvib
vib  h j  nj  
j  2
3686 cm-1 3725 cm-1
物理化學(三) 應用化學系朱超原老師 28
The total energy
The energy of a molecule is expressed as the sum of each degree of freedom

tot  trans rot vib elec

2  2
n 2 2  nvib
 1
vib  h j  nj  
h  nx n z 
Enx n y nz   
y

8m  a 2 b 2 c 2  j  2
n x , n y , n z  1,2,3, 

2
J  J  J  1, J  0,1,2, 
2I
for linear molecule
物理化學(三) 應用化學系朱超原老師 29
Relative energy level spacing
The general trend in energy spacing:
Electronic > Vibrations > Rotations >> Translation

 3

 2
 1
00  0

J 2

r J 1
D0

De
J 0

物理化學(三) 應用化學系朱超原老師 30
 I-4. Partition function
Energy from molecular level
Partition function
 E j k BT
Q V , N , T   e
j

  ln Q 
Energy U  k BT  2

 T V ,N
  ln Q 
Pressure P  k BT 2
 
  V T ,N

  ln Q 
S  k BT    k B ln Q
Entropy  T V ,N
物理化學(三) 應用化學系朱超原老師 31
Methods for solving partition function

Quantum  wave function

Classical  classical trajectory

Semiclassical  wave function obtained by

classical trajectory

物理化學(三) 應用化學系朱超原老師 32