Professional Documents
Culture Documents
Darin J. Ulness
1 Quantum Theory 16
1.1 The “Fall” of Classical Physics . . . . . . . . . . . . . . . . . . . . 16
1.2 Bohr’s Atomic Theory . . . . . . . . . . . . . . . . . . . . . . . . 17
1.2.1 First Attempts at the Structure of the Atom . . . . . . . . 17
4 Particle in a Box 31
4.1 The 1D Particle in a Box Problem . . . . . . . . . . . . . . . . . . 31
4.2 Implications of the Particle in a Box problem . . . . . . . . . . . 34
i
5.2 Spectroscopy (An Introduction) . . . . . . . . . . . . . . . . . . . 42
6 Hydrogenic Systems 46
6.1 Hydrogenic systems . . . . . . . . . . . . . . . . . . . . . . . . . . 46
6.2 Discussion of the Wavefunctions . . . . . . . . . . . . . . . . . . . 49
6.3 Spin of the electron . . . . . . . . . . . . . . . . . . . . . . . . . . 51
6.4 Summary: the Complete Hydrogenic Wavefunction . . . . . . . . 52
7 Multi-electron atoms 55
7.1 Two Electron Atoms: Helium . . . . . . . . . . . . . . . . . . . . 55
7.2 The Pauli Exclusion Principle . . . . . . . . . . . . . . . . . . . . 56
7.3 Many Electron Atoms . . . . . . . . . . . . . . . . . . . . . . . . 58
7.3.1 The Total Hamiltonian . . . . . . . . . . . . . . . . . . . . 59
15 Work 107
15.1 Properties of Partial Derivatives . . . . . . . . . . . . . . . . . . . 107
15.1.1 Summary of Relations . . . . . . . . . . . . . . . . . . . . 107
15.2 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
15.2.1 Types of Systems . . . . . . . . . . . . . . . . . . . . . . . 108
15.2.2 System Parameters . . . . . . . . . . . . . . . . . . . . . . 109
15.3 Work and Heat . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
15.3.1 Generalized Forces and Displacements . . . . . . . . . . . 110
15.3.2 P V work . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
21 Equilibrium 151
21.0.3 Equilibrium constants in terms of KC . . . . . . . . . . . . 153
21.0.4 The Partition Coefficient . . . . . . . . . . . . . . . . . . . 153
23 Ionics 161
23.1 Ionic Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
23.1.1 Ionic activity coefficients . . . . . . . . . . . . . . . . . . . 162
23.2 Theory of Electrolytic Solutions . . . . . . . . . . . . . . . . . . . 163
23.3 Ion Mobility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
23.3.1 Ion mobility . . . . . . . . . . . . . . . . . . . . . . . . . . 165
27 Operators 187
27.1 Operator Algebra . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
27.2 Orthogonality, Completeness, and the Superposition Principle . . 191
46 Solutions 308
46.1 Measures of Composition . . . . . . . . . . . . . . . . . . . . . . . 308
46.2 Partial Molar Quantities . . . . . . . . . . . . . . . . . . . . . . . 308
46.2.1 Notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
46.2.2 Partial Molar Volumes . . . . . . . . . . . . . . . . . . . . 310
46.3 Reference states for liquids . . . . . . . . . . . . . . . . . . . . . . 311
46.3.1 Activity (a brief review) . . . . . . . . . . . . . . . . . . . 311
46.3.2 Raoult’s Law . . . . . . . . . . . . . . . . . . . . . . . . . 312
46.3.3 Ideal Solutions (RL) . . . . . . . . . . . . . . . . . . . . . 314
46.3.4 Henry’s Law . . . . . . . . . . . . . . . . . . . . . . . . . . 316
46.4 Colligative Properties . . . . . . . . . . . . . . . . . . . . . . . . . 318
46.4.1 Freezing Point Depression . . . . . . . . . . . . . . . . . . 318
46.4.2 Osmotic Pressure . . . . . . . . . . . . . . . . . . . . . . . 319
1
Solved Problems
Even though there aren’t many “book” problems assigned during the year, you can
still learn a lot be working these and looking that their solutions in the solution
manual.
Keep in mind this chapter provides some examples of how to solve problems for
both physical chemistry I and physical chemistry II. Consequently early in the
course some of the examples might seem very itimidating. Simply skip those
examples as you scan through this chapter.
Working problem sets is the heart and sole of learning physical chemistry. The
only way that you can be sure that you understand a concept at to be able to
solve the problems associated with it.
But there are some things that you can do to help yourself with these problems.
Tips
2
1. Remember nobody cares if you solve any particular problem on the problem
set. They have all been solved before, so if you solve them you will not
become famous nor will you save the world. The only reason you work them
is to learn.
2. Budget your time so that you don’t have to work on an overwhelming number
of problems at a time. Try to whip-off a few on the same day that you get
the problem set. Then work on them consistently during the week. This
will make the problem sets much more efficient at helping you learn.
3. You can do the problem. I don’t assign problems that you cannot do. If you
think you can’t do the problem then maybe you need try a different way of
thinking about it.
4. Part of the trouble is simply understanding what the problem is asking you
to do. There is a tendency to try to start solving the problem before fully
understanding the question.
3
• Do the math; either you will be able to do this or you won’t. It might
take some review on your part.
• Always check to see if the math makes sense when you are done.
• Make sure that the physical idea that you are using in your argument is
correct. If you are not sure, start with a related concept that is better
known by you.
• Look for self-consistency. Does you final answer jive with what you
know.
• f (x) = sin2 x
• f (x) = cos x
• f(x) = e−2ix
Solution: For the first function it is easiest to see the periodicity by writing the
function as f (x) = (sin x)(sin x). We know that this function will repeat zeros
when ever sin x = 0. This occurs at x = nπ, n = 0, ±1, ±2 . . ., so the periodicity
is π. The second function we should remember from trig as having a period of 2π.
Finally for the last function it is best to used Euler’s identity and write
The real part of this function, cos 2x, has a period of π as does the imaginary
part, sin 2x. Therefore the entire function has a period of π.
4
Problem: Which of the following functions are eigenfunction of the momentum
d
operator, p̂x = −i~ dx .
• ψ(x) = eikx
2
• ψ(x) = e−αx
• ψ(x) = cos kx
2
Problem: A quantum object is described by the wavefunction ψ(x) = e−αx .
What is the probability of finding the object further than α away from the origin
( x = 0)?
5
Solution: First of all we do not know if this wavefunction is normalized, so we
should assume that it isn’t. We could normalize this wavefunction, but we won’t.
We are interested in finding the probability that the object is outside of the region
−α < x < α. To do this using an unnormalized wavefunction we must evaluate
R −α 2 R∞
−∞
|ψ(x)| dx + α
|ψ(x)|2 dx
P (|x| > α) = R∞ . (5)
−∞
|ψ(x)|2 dx
The first integral in the numerator gives the probability that the object is at a
position x < −α and the second integral in the numerator gives the probability
for x > α. The denominator accounts for the fact that the wavefunction is un-
normalized. The limits of the integral in the denominator represent all space for
the object. If you were working with a normalized wavefunction the denominator
would be equal to 1 and hence not needed. Plugging in the wavefunctions we have
R −α −2αx2 R∞ 2
−∞
e dx + α e−2αx dx
P (|x| > α) = R ∞ . (6)
−∞
e−2αx2 dx
Mathematica can assist with these integrals to give the final answer of
√ 3
P (|x| > α) = erfc[ 2α 2 ]. (7)
Solution: Following our general procedure from the notes if we have some unnor-
malized wavefunction, ψunnorm we know that this function must simply be some
constant N multiplied by the normalized version of this function:
6
Which for this case is
sZ sZ r
∞ ∞
1
N= |e−γx |2 dx = e−2γx dx = (10)
0 0 2γ
So finally we get the normalized wavefunction by rearanging ψunnorm = Nψnorm :
p
ψnorm (x) = 2γe−γx . (11)
Remember the extra r2 sin θ is needed when integrating in spherical polar coordi-
nates. The normalized 1s wavefunction is
1
ψ1s = p 3 er/a0 . (15)
πa0
7
We can do this integral by hand or have Mathematica help us to give
5
P (r > a0 ) = = 0.677. (16)
e2
So, about 68% of the time the electron would be found at some distance greater
then one Bohr radius from the proton.
Solution: This problem appears hard at first since we are not studying three
dimensional systems, but all it is asking is to express the wavefunction, which is
a function of the three spatial dimensions, Ψ(x, y, z) as a product state. We know
that if the wavefunction is to be a product state then the Hamiltonian must be
made up of a sum of independent terms. To see this we write out the Laplacian
to get µ ¶
−~2 ∂ 2 ∂2 ∂2
Ĥ = + + . (17)
2m ∂x2 ∂y 2 ∂z 2
We see that indeed the Hamiltonian is a sum of term that depends only on x,
a term depending only on y and a term that depends only on z. Therefore the
appropriate product state is
Problem: Expand the Morse potential in a Taylor’s series about Req . Verify that
the coefficient for the linear term is zero. What is the force constant associated
with the Morse potential?
8
The Taylor series about Req for this function is
¯ ¯
dV (x) ¯¯ 1 d2 V (x) ¯¯
V (x) = V (x)|Req + (R − Req ) + (R − Req )2 + · · · . (20)
| {z } dx ¯Req 2! dx2 ¯Req
=0 | {z } | {z }
=0 = β 2 De
So, yes the coefficient of the linear term (the term involving (R − Req ) to the
first power) is zero. This will always be true when you perform a Taylor series
expansion about a minimum (or maximum). The force constant is given by the
coefficient of the quadratic term so in this case k = β 2 De .
Solution: This problem requires the we think qualitatively about the wavefunc-
tions and the potentials for the harmonic oscillator and the Morse oscillator. The
potential for the harmonic oscillator is described by a parabola centered about the
equilibrium bond length. Hence no mater what the vibrational quantum number is
there is just as much of the wavefunction on either side equilibrium thus hRi = Req
for any quantum number. The Morse potential does not have this symmetry. It
is steeper on the “short” side of equilibrium and softer on the “long” side of equi-
librium and this “softness” increases with increasing quantum number. Therefore
without performing any calculations we can at least say that hRi increases as the
quantum number increases.
9
many are in the first excited state of the symmetric C—H vibrational mode (3063
cm −1 )?
Solution: This is a problem that deals with the Boltzmann distribution. So,
µ ¶ ³ ´
992 3×992
rb
Nv=1 = 2 sinh × e− 2×208 × 1020 = 8.41 × 1017 (21)
2 × 208
and µ ¶ ³ ´
C—H 3063 − 3×3063
Nv=1 = 2 sinh × e 2×208 × 1020 = 4.02 × 1013 . (22)
2 × 208
17
We see that about 8.41×10
1020
× 100% = 0.841% of the benzene molecules are in the
13
first vibrational excited state for the ring breathing mode and 4.02×10
1020
× 100% =
0.0000402% of the benzene molecules are in the first excited state for the C—H
stretching mode.
Problem: Consider a linear chain of N atoms. Each of the atoms can be in one
of three states A, B or C, except that an atom in state A can not be adjacent to
an atom in state C. Find the entropy per atom for this system as N → ∞. To
solve this problem it is useful to define the set of three dimensional column vectors
V (j) such that the three elements are the total number of allowed configurations of
a j-atom chain having the j th atom in state A, B or C. For example,
⎡ ⎤ ⎡ ⎤ ⎡ ⎤
1 2 5
(1) ⎢ ⎥ (2) ⎢ ⎥ (3) ⎢ ⎥
V = ⎣ 1 ⎦, V = ⎣ 3 ⎦, V = ⎣ 7 ⎦,··· . (23)
1 2 5
The V (j+1) can be found from the V (j) vector using the matrix equation,
10
The matrix M is the so-called transfer matrix for this system. It can be shown
that the number of configurations W = Tr[M N ]. Now for large N, Tr[M N ] ≈ λN
max ,
where λmax is the largest eigenvalue of M. So
W = lim λN
max . (26)
N→∞
Solution: For part (a) we simply use the transfer matrix as directed in the
problem (we are given V (3) ):
⎡ ⎤⎡ ⎤ ⎡ ⎤
1 1 0 5 12
(4) ⎢ ⎥⎢ ⎥ ⎢ ⎥
V =⎣ 1 1 1 ⎦ ⎣ 7 ⎦ = ⎣ 17 ⎦ .
0 1 1 5 12
For part (b) we need to list all states for the case of N = 3 and verify the we get
the same result as calculated using the transfer matrix. Remembering that V (3)
gives us the number of sequences that end in a given state we should organize our
list in the same manner
States ending in A States ending in B States ending in C
AAA AAB ABC
ABA ABB BBC
BAA BAB BCC
BBA BBB CBC .
CBA BCB
CBB
CCB
√ √ √
5 states 7 states 5 states
11
States like AAC are not allowed because A and C are neighbors.
For part (c) we evaluate W = Tr[M N ] for N = 1 and 2. For N = 1, W =
Tr[M] = 3 This corresponds to the three distinguishable microstates A, B, and
C. For N = 2,
⎡⎡ ⎤⎡ ⎤⎤ ⎡⎡ ⎤⎤
1 1 0 1 1 0 2 2 1
⎢⎢ ⎥⎢ ⎥⎥ ⎢⎢ ⎥⎥
W = Tr[M 2 ] = Tr ⎣⎣ 1 1 1 ⎦ ⎣ 1 1 1 ⎦⎦ = Tr ⎣⎣ 2 3 2 ⎦⎦ = 7 (27)
0 1 1 0 1 1 1 2 2
This corresponds to the seven distinguishable microstates AA, AB, BA, BB, BC,
CB and CC (Remember C and A cannot be neighbors).
For part (d) we use
S k k k
= ln W = lim ln λN
max = lim N ln λmax = k ln λmax . (28)
N N N→∞ N N→∞ N
So, we simply need to find the maximum eigenvalue of the Transfer matrix. Using
√
Mathematica we find λmax = 1 + 2. Therefore the limiting entropy per atom
is ³
S √ ´
= k ln 1 + 2 . (29)
N
Problem: Using the classical theory of light scattering, calculate the positions of
the Rayleigh, Stokes and anti-Stokes spectral lines for benzene. Assume benzene
has only two active modes (992cm −1 and 3063cm −1 ) and assume the Laser light
used to do the scattering is at 20000cm −1 (this is 500nm–green light).
Solution: Since there are two vibrational modes we expect two Stokes lines to
the red of 20000cm−1 , one at 20000cm−1 − 992cm−1 = 19008cm−1 and one at
20000cm−1 − 3063cm−1 = 16937cm−1 . Likewise we expect two anti-Stokes lines,
one at 20000cm−1 + 992cm−1 = 20992cm−1 and one at 20000cm−1 + 3063cm−1 =
23063cm−1 . There is only one Rayleigh line and it is at the same frequency at the
input laser beam which, in this case, is 20000cm−1 .
12
Problem: A simple model for a crystal is a “gas” of harmonic oscillators. De-
termine A, S, and U from the partition function for this model.
13
¡ ¢ ¡ ∂U ¢
Now ∂U∂T V
is just heat capacity, CV , but ∂V T
is nothing convenient so we must
proceed. We employ the “useful relation”
µ ¶ µ ¶
∂U ∂P
=T −P (36)
∂V T ∂T V
to eliminate U in favor of P so that we can use the equation of state for a Berthelot
gas. One obtains
µ ¶ µ ¶
∂P nR n2 a nRT n2 a 2n2 a
T −P =T + 2 2 − + = . (37)
∂T V V − nb T V V − nb T V 2 TV 2
2n2 a
dU = CV dT + dV (38)
TV 2
¡ ∂P ¢
Problem: Use the identities for partial derivatives to eliminate the ∂T V
factor
in µ ¶ µ ¶
∂V ∂P
Cp = Cv + T (39)
∂T P ∂T V
so that all derivatives are at constant pressure or temperature.
14
Part I
15
15
1. Quantum Theory
A good theory:
• self consistent
• predictive
Around the turn of the century, experiments were being performed in which the re-
sults defied explanation by means of the current understanding of physics. Among
these experiments were
16
16
5. The two slit experiment
∗ ∗ See Handouts ∗ ∗
• The electron orbits the nucleus with the attractive coulomb force balanced
by the repulsive centrifugal force.
17
— As the electron orbits the nucleus, the atom acts as an oscillating dipole
18
• Atoms don’t collapse =⇒ what are the consequences
Experimental clues
• If the orbital radius was continuous the gas would have a continuous spec-
trum.
2
The constant quantity 4π 0~
me e2
appears often and is given the special symbol a0 ≡
4π 0 ~ 2
me e2
= 0.52918 Å and is called the Bohr radius.
The total energy of the Bohr atom is related to its quantum number
µ 2 ¶
2 e 1
EN = −Z . (1.2)
2a0 N 2
Tests of the Bohr atom
19
2
e
— Eionize = 2a 0
= 13.606 eV = 109,667 cm−1 = R. R is called the Rydberg
constant.
— Eionize experimentally observed from spectroscopy is 13.605 eV (very
good agreement)
• — Since the orbitals are quantized, the atom may only change its orbital
radius by discrete amounts.
— Doing this results in the emission or absorption of a photon with energy
4E
ṽ = (1.5)
hc
20
• Spin is not included in theory
The Bohr quantization idea points to a wavelike behavior for the electron.
The wave must satisfy periodic boundary conditions much like a vibrating ring
The Bohr atom was an important step towards the formulation of quantum theory
21
2. The Postulates of Quantum
Mechanics
2.1. Postulate I
That is, the probability of finding a particle which is described by ψ(x, y, z) at the
position between x and x+dx, y and y +dy and z and z +dz is |ψ(x, y, z)|2 dxdydz
(or |ψ(r, θ, φ)|2 r2 sin θdrdθdφ in spherical coordinates).
22
22
Properties of the wavefunction
• Single valueness
23
The N is just a constant so it can be pulled out of both the mod-square and the
integral Z Z
2
|ψunnorm | dxdydz = N 2
|ψnorm |2 dxdydz, (2.3)
space space
but Z
|ψnorm |2 dxdydz = 1 (2.4)
space
This gives us an expression for N. Taking the square root of both sides gives.
sZ
N= |ψunnorm (x, y, z)|2 dxdydz. (2.6)
space
To find the probability for the particle to be in a finite region of space we simple
evaluate (here a 1D case)
R x2 Z x2
x1
|ψ(x)|2 dx if ψ(x)
P (x1 < x < x2 ) = R ∞ 2 =⇒ |ψ(x)|2 dx (2.8)
−∞
|ψ(x)| dx normalized x1
24
An operator takes a function and turns it into another function
This is just like how a function takes a number and turns it into another number.
• x̂ = x
∂
• p̂x = −i~ ∂x
and of course the analogous operators for the other coordinates (y, z) and coordi-
nate systems (spherical, cylindrical, etc.).
Nearly all operators we will need are algebraic combinations of the above.
Postulate III: The measurement of a physical observable will give a result that
is one of the eigenvalues of the corresponding operator.
For a given operator only a special set of function satisfy this equation. These
functions are called eigenfunctions.
25
The number that goes with each function is called the eigenvalue.
Example
Let Ô in the eignevalue equation be the operator that takes the derivative: Ô =
dˆ = dx
d
.
So we want a solution to
ˆ (x) = λf (x)
df (2.11)
df (x)
= λf (x)
dx
So, we ask ourselves what function is proportional to its own derivative? ⇒
f (x) = eλx .
So the eigenfunctions are the set of functions f (x) = eλx and the eigenvalues are
the numbers λ
26
3. The Setup of a Quantum
Mechanical Problem
The operator associated with the total energy is called the Hamiltonian operator
(or simply the Hamiltonian) and is given the symbol Ĥ.
This equation is the most important equation of the course and we will use it many
times throughout our discussion of quantum mechanics and statistical mechanics.
Nearly every problem one is faced with in elementary quantum mechanics is han-
dled by the same procedure as given in the following steps.
27
27
• The total energy for a classical system is
Ecl = T + V, (3.2)
V = V (x, y, z) (3.4)
• Note: Some quantum systems don’t have classical analogs so the Hamil-
tonian operator must be hypothesized.
So,
−~2 2
Ĥ = T̂ + V̂ = ∇ + V (x, y, z) (3.7)
2m
3. Solve the Schrödinger equation, Ĥψ = Eψ, which is now a second order
differential equation of the form
∙ 2 ¸
−~ 2
∇ + V (x, y, z) ψ = Eψ
2m
−~2 2
⇒ ∇ ψ + (V (x, y, z) − E) ψ = 0 (3.8)
2m
28
• Note: It is solely the form of V (x, y, z) which determines whether this
is easy or hard to do.
• For one-dimensional problems
−~2 d2
ψ + (V (x) − E) ψ = 0 (3.9)
2m dx2
For example,
Z Z
hx̂i = ∗
ψ x̂ψdxdydz = x |ψ|2 dxdydz (3.11)
space space
and Z Z
∗ ∂ψ
hp̂x i = ψ p̂x ψdxdydz = −i~ ψ∗ dxdydz (3.12)
space space ∂x
29
3.4. The Heisenberg Uncertainty Principle
Suppose we know the position of a particle perfectly, what can we say about its
momentum?
30
4. Particle in a Box
We now will apply the general program for solving a quantum mechanical problem
to our first system: the particle in a box.
This system is very simple which is one reason for beginning with it. It also can
be used as a “zeroth order” model for certain physical systems.
We shall soon see that the particle in a box is a physically unrealistic system and,
as a consequence, we must violate one of our criteria for a good wavefunction.
Nevertheless it is of great pedagogical and practical value.
31
31
Now, in region I and III, where the potential is infinite, the particle can never
exist so, ψ must equal zero in these regions.
−~2 d2 ψ(x)
Ĥψ = Eψ =⇒ = Eψ, (4.2)
2m dx2
which can be rearranged into the form
d2 ψ(x) 2mE
+ 2 ψ(x) = 0. (4.3)
dx2 ~
The general solution of this differential equation is
Now ψ must be continuous for all x. Therefore it must satisfy the boundary
conditions (b.c.): ψ(0) = 0 and ψ(a) = 0.
32
From the ψ(0) = 0 b.c. we see that the constant B must be zero because
cos kx|x=0 = 1.
As can be inferred from the following figure, the second b.c., ψ(a) = 0, places
certain restrictions on k.
In particular,
nπ
kn =, n = 1, 2, 3, · · · . (4.5)
a
The values of k are quantized. So, now we have
nπx
ψn (x) = A sin . (4.6)
a
33
Solving for A gives r
2
A= . (4.9)
a
q
2mEn nπ
We can get the energy levels from kn = ~2
and kn = a
:
n2 π 2 ~2 ~= 2π
h
n2 h2
En = = . (4.11)
2ma2 8ma2
34
The smallest value for n is 1 which corresponds to an energy of
h2
E1 = 6= 0. (4.12)
8ma2
That is, the lowest energy state, or ground state, has nonzero energy. This residual
energy is called the zero point energy and is a consequence of the uncertainty
principle.
If the energy was zero then we would conclude that momentum was exactly zero,
δ p̂ = 0. But we also know that the particle is located within a finite region of
space, so δx̂ 6= ∞.
(n + 1)2 h2 n2 h2 2 2 h2
4E = En+1 − En = − = /
(n + 2n + 1 − /
n )
8ma2 8ma2 8ma2
h2
4E = (2n + 1) (4.13)
8ma2
35
−~ 2 d2 d2
The operator for kinetic energy is T̂ = 2m dx2
. The important part of this is dx2
.
From freshman calculus we know that the second derivative of a function describes
its curvature so, a wavefunction with more curvature will have a larger second
derivative and hence it will posses more kinetic energy.
Applying this idea to the particle in a box we an anticipate both zero point energy
and the behavior of the energy levels with increasing a.
• We know the wavefunction is zero in regions I and III. We also know that
the wave function is not zero everywhere. Therefore it must do something
between x = 0 and x = a. It must have some curvature and hence some zero
point energy.
The particle in a box problem illustrates some of the many strange features of
quantum mechanics.
We have already seen such nonclassical behavior as quantized energy and zero
point energy.
36
yet the probability of finding the particle at x = a2 is zero: ψ2 ( a2 ) = 0. There is
a node at x = a2 . So even though the particle may be found anywhere else in the
box and it may get from the left side of the node to the right side, it can never
be found at the node.
37
5. The Harmonic Oscillator
The harmonic oscillator model which is simply a mass undergoing simple harmonic
motion. The classical example is a ball on a spring
The harmonic oscillator is arguably the single most important model in all of
physics.
We shall begin by reviewing the classical harmonic oscillator and than we will
turn our attention to the quantum oscillator.
The force exerted by the spring in the above figure is F = −k(R − Req ), where k
is the spring constant and Req is the equilibrium position of the ball.
38
38
2
From Newton’s law of motion F = ma = m ddt2x , we get
d2 x d2 x k
m 2 = −kx ⇒ 2 + x = 0 (5.1)
dt dt m
This is second order differential equation which we already know the solutions to:
For quantum mechanics it is much more convenient to talk about energy rather
than forces, so in going to the quantum oscillator, we need to express the force of
the spring in terms of potential energy V . We know
Z
1
V = − F dx = kx2 + C. (5.3)
2
This differential equation is not easy to solve (you can wait to solve it in graduate
school).
39
The equation is very close to the form of a know differential equation called Her-
mite’s differential equation the solutions of which are called the Hermite polynom-
inals.
As it turns out, the solutions (the eigenfunctions) to the Schrödinger equation for
the harmonic oscillator are
µ ¶1
2
− y2 km 4 1
ψn (y) = An Hn (y)e , y = 2
x, An = p √ , (5.6)
~ 2n n! π
where An is the normalization constant for the nth eigenfunction and Hn (y) are
the Hermite polynomials.
40
1. Consider the ground state (the lowest energy level)
• The wavefunctions penetrate into the region where the classical particle
is forbidden to go
— The wavefunction is nonzero past the classical turning point.
• The probability distribution |ψ|2 becomes more and more like what is
expected for the classical oscillator when v → ∞.
— This is a manifestation of the correspondence principle which
states that for large quantum numbers, the quantum system must
behave like a classical system. In other words the quantum me-
chanics must contain classical mechanics as a limit.
41
• Remember the wavefunctions are time independent and the energy lev-
els are stationary
• If a molecule is in a particular vibrational state it is NOT vibrating.
The primary method of measuring the energy levels of a material is through the
use of electromagnetic radiation.
Atoms and molecules absorb or emit light only at specific (quantized) energies.
These specific values correspond to the energy level difference between the initial
and final states.
42
Key Equations for Exam 1
Listed here are some of the key equations for Exam 1. This section should not
substitute for your studying of the rest of this material.
The equations listed here are out of context and it would help you very little to
memorize this section without understanding the context of these equations.
The equations are collected here simply for handy reference for you while working
the problem sets.
Equations
• The short cut for getting the normalization constant (1D, see above for 3D).
sZ
N= |ψunnorm (x)|2 dx. (5.9)
space
43
43
• The Schrödinger equation for 1D problems as a differential equation,
−~2 d2
ψ + (V (x) − E) ψ = 0. (5.12)
2m dx2
• How to get the average value for some property (1D version),
Z
hα̂i = ψ∗ α̂ψdx. (5.13)
space
44
Part II
45
45
6. Hydrogenic Systems
Now that we have developed the formalism of quantum theory and have discussed
several important systems, we move onto the quantum mechanical treatment of
atoms.
Hydrogen is the only atom for which we can exactly solve the Schrödinger equation
for. So this will be the first atomic system we discuss.
The Schrödinger equation for all the other atoms on the periodic table must be
solved by approximate methods.
Hydrogenic systems are those atomic systems which consist of a nucleus and one
electron. The Hydrogen atom (one proton and one electron) is the obvious exam-
ple
These system are centrosymmetric. That is they are completely symmetric about
the nucleus.
The obvious choice for the coordinate system is to use spherical polar coordinates
46
46
with the origin located on the nucleus.
−Ze2
V (r) = . (6.1)
(4π 0 )r
So the Hamiltonian is
−~2 ˆ 2 −Ze2
Ĥ = ∇ + . (6.2)
2me (4π 0 )r̂
Schrödinger’s equation (in spherical polar coordinates) becomes
Eψ = Ĥψ (6.3)
µ 2 2
¶
−~ ˆ 2 −Ze
Eψ = ∇ + ψ
2me (4π 0 )r̂
µ 2∙ µ ¶¸ ¶
−~ 1 ∂ 2 ∂ 1 1 ∂ ∂ 1 ∂2 −Ze2
Eψ = r + sin θ + + ψ
2me r2 ∂r ∂r r2 sin θ ∂θ ∂θ sin2 θ ∂φ2 (4π 0 )r
The Hamiltonian is (almost) the sum of a radial part (only a function of r) and
an angular part (only a function of θ and φ):
1
Ĥ = Ĥrad + Ĥang , (6.4)
r2
∙ ¸
−~2 1 ∂ 2 ∂ Ze2
Ĥrad = r − (6.5)
2me r2 ∂r ∂r (4π 0 )r
and µ ¶
−~2 1 ∂ ∂ 1 ∂2
Ĥang = sin θ + (6.6)
2me sin θ ∂θ ∂θ sin2 θ ∂φ2
Since the Hamiltonian is the sum of two terms, ψ must be a product state.
47
yields
ψ ang (θ, φ) = Ylm (θ, φ), (6.9)
where the Ylm (θ, φ)’s are the spherical harmonic functions characterized by quan-
tum numbers l and m. The spherical harmonics are known functions. (Mathematica
knows them and you can use them just like any other built-in function like sine
or cosine.)
We shall use the spherical harmonics more next semester when we develop the
quantum theory of angular momentum.
It also turns out that the energy associated with Ĥang is found to be
l(l + 1)~2
E = El = . (6.10)
2me
So,
l(l + 1)~2
Ĥang ψang (θ, φ) = ψang (θ, φ) (6.11)
2me
Now let’s denote the radial part of the wavefunction as ψ rad (r) = R(r).
48
The Ylm (θ, φ) can now be cancelled to leave a one dimensional differential equation:
µ ¶
−~2 1 ∂ 2 ∂ Ze2 l(l + 1)
r − − R(r) = ER(r). (6.14)
2me r2 ∂r ∂r 4π 0 r r2
This differential equation is very similar to a known equation called Laguerre’s
differential equation which has as solutions the Laguerre polynomials Lln (x).
In fact, the solutions to our differential equation are closely related to the Laguerre
polynomials.
µ ¶l µ ¶
2σ −σ/n 2l+1 2σ
Rnl (σ) = Anl e Ln+1 , (6.15)
n n
where the normalization constant, Anl , depends on the n and l quantum numbers
as sµ ¶3
2Z (n − l − 1)!
Anl = − (6.16)
na0 2n[(n + l)!]3
The energy eigenvalues, i.e., the energy levels are given by
Z 2R
En = − (6.17)
n2
Note: The energy levels are determined by n alone–l drops out.
Also Note: the energy levels are the same as for the Bohr model.
So, the total wavefunction that describes a hydrogenic system (ignoring the spin
of the electron, which will be briefly discussed later) is
We are now very close to having the atomic orbitals familiar from freshman chem-
istry.
49
We have explicitly derived the “physicists” picture of the atomic orbitals
The wavefunctions in the “physicists” picture are complex (they have real and
imaginary components). The wavefunctions that chemists like are pure real. So
one needs to form linear combinations of these orbitals such that these combina-
tions are pure real.
The atomic orbital you are used to from freshman chemistry are the “chemists”
picture of atomic orbitals
In the above table ψ1s , ψ 2s , ψ 2p0 , ψ 3d0 are pure real and so these are the same in
the “chemists” picture as in the “physicists” picture.
The table below lists the atomic orbitals in the “chemists” picture as linear com-
binations of the “physicists” picture wave functions.
50
orbital n l m wavefunctions (σ = r/a0 )
1s 1 0 0ψ1s = ψ1s
2s 2 0 0ψ2s = ψ2s
2p 2 1 0ψpz = ψ2p0
£ ¤
2 1 ψ2px = √12 ψ2p1 + ψ2p−1
±1
£ ¤
2 1 ±1 ψ2py = i√1 2 ψ2p1 − ψ2p−1
3d 3 2 0 ψ3dz2 = ψ3d0
£ ¤
3 2 ±1 ψ3dxz = √12 ψ3d1 + ψ3d−1
£ ¤
3 2 ±1 ψ3dyz = i√1 2 ψ3d1 − ψ3d−1
£ ¤
3 2 ±2 ψ3dxy = √12 ψ3d2 + ψ3d−2
£ ¤
ψ3dx2 −y2 = i√1 2 ψ3d2 − ψ3d−2
Spin is actually rather peculiar so we will put off a more detailed discussion until
next semester.
The spin wavefunction is a function in spin space not the usual coordinate space,
so we can not write down an explicit function of the coordinate space variables.
51
We simply denote the spin wavefunction generally as χs,ms and “tack it on” as
another factor of the complete wavefunction.
• The principle quantum number, n: determines the total energy of the sys-
tems and the atomic shells.
52
— The angular momentum quantum number, l, can take on values of 0,
1, . . . (n − 1)
— For historical reasons l = 0 is called s, l = 1 is called p, l = 2 is called
d, l = 3 is called f etc.
• The spin quantum number, s: determines the total spin angular momentum.
We have accomplished quite a bit. We have determined all that we can about the
hydrogen atom within Schrödinger’s theory of quantum mechanics.
This is not the full story however. The Schrödinger theory is a non-relativistic
one; that is, it can not account for relativistic effects which show up in spectral
data. We also had to add spin in an ad hoc manner to account for what we know
experimentally–spin did not fall out of the theory naturally.
Dirac, in the late 1920’s, developed a relativistic quantum theory in which the
well established phenomenon of spin arose naturally. His theory also made the
53
bold prediction of the existence anti-matter that has now been verified time and
again.
The Dirac theory was still not fully complete, because there still existed exper-
imental phenomena that was not properly described. In 1948 Richard Feynman
developed the beginnings of quantum electrodynamics (QED). QED is the best
theory ever developed in terms of matching with experimental data.
Both the relativistic Dirac theory and QED are beyond our reach, so we limit
ourselves to the non-relativistic Schrödinger theory.
54
7. Multi-electron atoms
We now consider a system consisting of two electrons and a nucleus; for example,
helium.
Although the extension from hydrogen to helium seems simple it is actually ex-
tremely complicated. In fact, it is so complicated that it can’t be solved exactly.
The electron—electron repulsion term is responsible for the difficulty of the prob-
lem. It makes a closed form solution impossible.
55
55
• Perturbation theory (next semester)
All physical properties of a system where we have labelled the electrons as, say, 1
and 2 must be exactly the same as when the electrons are labelled 2 and 1.
The Pauli exclusion principle states: The total wavefunctions for fermions
(e.g., electrons) must be antisymmetric under the exchange of indistinguishable
fermions.
Note: a similar statement exists for bosons (e.g., photons): The total wavefunction
for bosons must be symmetric under exchange of indistinguishable bosons.
56
The total wavefunction is
Ψ = ψ(1, 2)χ(1, 2) (7.3)
Since a complete solution for helium is not possible we must use approximate
wavefunctions. Since we are doing this, we may as well simplify matters and use
product state wavefunctions (products of the hydrogenic wavefunctions).
Ψ = ψ(1)ψ(2)χ(1)χ(2), (7.4)
| {z }| {z }
spatial part spin part
where the single particle wavefunctions are that of the hydrogenic system.
The Pauli exclusion principle implies that if the spatial part is even with respect
to exchange then the spin part must be odd. Likewise if the spatial part is odd
then the spin part must be even.
Now let’s blindly list all possibilities for the ground state wave function of helium
These appear to be four reasonable ground state wavefunctions which would im-
ply a four-fold degeneracy. However considering the symmetry with respect to
exchange we see the following
• Ψa has symmetric spatial and spin parts and is there for symmetric. It must
be excluded.
• Similarly for Ψd .
• Ψb and Ψc have symmetric spatial parts, but the spin part is neither sym-
metric or antisymmetric. So, one must make an antisymmetric linear com-
bination of the spin parts.
57
The appropriate linear combination is
The remaining atoms on the periodic table are handled in a manner similar to
helium.
The product wavefunction for the ground state is determined by applying the
aufbau principle. The aufbau principle states that the ground state wavefunction
is built-up of hydrogenic wavefunctions
58
The reason one can be sure that this wavefunction is the antisymmeterized is that
we know from linear algebra that the determinant is antisymmetric under exchange
of rows (corresponds to exchanging two electrons). It is also antisymmetric under
exchange of columns.
Another property of the determinant is that if two rows are the same (corresponds
to two electrons in the same state) the determinant is zero. This agrees with the
Puli exclusion principle.
or ¯ ¯
¯ ψ (1)α(1) ψ (1)β(1) ψ (1)β(1) ¯
¯ 1s 1s 2s ¯
¯ ¯
Ψ2 = ¯ ψ1s (2)α(2) ψ1s (2)β(2) ψ2s (2)β(2) ¯ (7.10)
¯ ¯
¯ ψ (3)α(3) ψ (3)β(3) ψ (3)β(3) ¯
1s 1s 2s
The total Hamiltonian for a many electron (ignoring spin-orbit coupling which
will be discussed next semester) atom is
" #
XN
−~2 2 Ze2 X e2
Ĥ = ∇ − + (7.11)
i=1
2me i 4π 0 ri j>i 4π 0 rij
59
8. Diatomic Molecules and the Born
Oppenheimer Approximation
Now that we have applied quantum mechanics to atoms, we are able to begin the
discussion of molecules.
This leaves three degrees of freedom (R, θ, φ) which describe the position of the
nuclei relative to the center of mass. R determines the internuclear separation
and θ and φ determine the orientation.
60
60
8.1.1. The Hamiltonian
P ~2 ˆ 2
T̂e = i − 2m e
∇ei is the kinetic energy operator for the electrons.
ZA ZBe e2
V̂NN = 4π 0 R
is the nuclear—nuclear potential energy operator.
P h ZA e2 ZB e2
i
V̂Ne = − i 4π 0 rAi
+ 4π 0 rBi
is the nuclear—electron potential energy operator.
P e2
V̂ee = i>j 4π 0 rji is the electron—electron potential energy operator.
61
8.1.2. The Born—Oppenheimer Approximation
Since the Hamiltonian is a sum of two terms, one can write the wavefunction
ψ(R, {ri }) as a product wavefunction
ψ = ψN ψe , (8.6)
62
The last equation is exactly like a Schrödinger equation with a potential equal to
Ee (R).
It is convenient at this point to expand Ee (R) in a Taylor series about the equi-
librium position, Req :
µ ¶ µ ¶
0 ∂E 1 ∂2E
Ee (R) = E + (R − Req ) + 2
(R − Req )2 + · · · . (8.9)
∂R Req 2! ∂R Req
Now E 0 is just a constant which, by choice of the zero of energy, can be set to an
arbitrary value.
¡ ∂E ¢
Since we are at a minimum, ∂R Req
must be zero, so the linear term vanishes.
³ ´
∂2E
One defines ∂R2
≡ ke as the force constant.
Req
63
As a first approximation we can neglect the anharmonicity. With this, the Schrödinger
equation becomes
∙ 2 2 ¸
~ ∂ 1 2
− + ke (R − Req ) ψvib = Evib ψvib . (8.10)
2μ ∂R2 2
And
1
Evib,n = hcω̃ e (n + ), (8.13)
2
q
1 ke
where ω̃ e ≡ 2π μ
.
For high energies we need a more realistic potential–one that will allow of bond
dissociation.
64
q
μ
where De is the well depth and β = 2πcω̃e 2D e
is the Morse parameter. Note:
this expression for the Morse potential has the zero of energy at the bottom of
the well (i.e. R = Req , ;Ee (Req ) = 0).
Now the zero of energy is the dissociated state (i.e. R → ∞, ;Ee (R → ∞) = 0).
We approach this quantum mechanical problem exactly like all the other.
As it turns out, this Schrödinger equation can be transformed into a one of a broad
class of known differential equations called confluent hypergeometric equations–
the solutions of which are the confluent hypergeometric functions, 1 F1 .
65
hcω̃ e
where ω̃ e xe together is the anharmonicity constant, with xe = 4De
.
∗ ∗ ∗ See Handout ∗ ∗∗
Infrared (IR) and Raman spectroscopy are the two most widely used techniques
to probe vibrational levels.
4E
The spectral peaks appear at ṽ = hc
(in units of wavenumbers, cm−1 ).
Since the energy levels depend on mass, isotopes will have a different transition
energy and hence appear in a different place in the spectrum. Heavier isotopes
have lower transition energies.
66
9. Molecular Orbital Theory and
Symmetry
One of the most important concepts in all of chemistry is the chemical bond.
We are now prepared to discuss a bonding theory that is more rigorously based
in quantum mechanics.
Basically we will treat the molecules in the same way as all our other quantum
mechanical problems (e.g., particle in a box, harmonic oscillator, etc.)
As you might expect, it is not possible to obtain the exact wavefunctions and
energy levels so, we must settle for approximate solutions.
The Hamiltonianfor H+
2 is
67
67
We use the Born-Oppenheimer approximation and treat the nuclear coordinates
as a parameters rather than as variables. So we only worry about parts of the
Hamiltonian that deal with the electron.
• Atomic orbitals: Hydrogen is the prototype and all other atomic orbitals
are built from the hydrogen atomic orbitals.
• Molecular orbitals: The hydrogen molecular ion is the prototype and all
other molecular orbitals are built from the hydrogen molecular ion molecular
orbitals.
There is one significant difference between the above, which is the hydrogen atomic
orbitals are exact whereas the hydrogen molecular ion molecular orbitals are not
exact.
In fact, we shall see that these molecular orbitals are constructed as linear com-
binations of atomic orbitals.
9.2. Symmetry
Let the atoms of the hydrogen molecular ion lie on the z-axis of the center of mass
coordinate system.
68
Inversion symmetry
• Because of the symmetry the electron density at (x, y, z) must equal the
electron density at (−x, −y, −z).
• The above symmetry therefore requires that the molecular orbitals be eigen-
functions of the inversion operator, ı̂. That is
• The terms gerade and ungerade apply only to systems that posses inversion
symmetry.
Cylindrical symmetry
69
• The cylindrical symmetry implies that the potential energy can not depend
on the φ.
70
• There is also a symmetry about the x-y plane called horizontal mirror plane
symmetry: operator σ̂ h .
• There are also vertical mirror plane symmetries, but we will put that dis-
cussion off for the time being.
71
10. Molecular Orbital Diagrams
Now that we know what symmetry the molecular orbitals must posses, we need
to find some useful approximations for them.
We will discuss the approximation which models the molecular orbitals as linear
combinations of atomic orbitals (LCAO).
Linear combination of the 1s atomic orbital from each H atom is used for the
molecular orbital of H+
2:
(1sA ) = ke−rA /a0 (10.1)
and
(1sB ) = ke−rB /a0 (10.2)
72
72
We construct two molecular orbitals as
and
Φ− = C− (1sA − 1sB ) (10.4)
The normalization condition is
Z
Φ± Φ± dΩ = 1 (10.5)
As can be seen from the above figure, Φ+ represents a situation in which the
electron density is concentrated between the nuclei and thus represents a bonding
orbital.
For molecular orbitals we shall also classify them according to angular momentum.
But we shall also classify them according to their inversion symmetry and wether
or not they are bonding or antibonding.
73
The classification according to angular momentum is as follows.
λ 0 ±1 ±2 · · ·
orbital symbol σ π δ ···
If the two atoms are infinitely far apart. The ground state of the system would
consist of two separate hydrogen molecules in their ground atomic states: (1s)1
74
As the atom are brought closer together, their respective s orbitals begin to over-
lap.
and
σ ∗u = 1sA − 1sB . (10.7)
75
It can be shown mathematically that the energy level associated with σg is lower
than σ∗u .
We can intuit this qualitatively however since the σ ∗u orbital must have a node
whereas the σ g does not.
The energy levels associated with the molecular orbitals are drawn schematically
is what is called a molecular orbital diagram.
Molecular orbital diagrams can be drawn for any molecule. Some get very compli-
cated. We will focus on the second row homonuclear diatomics and some simple
heteronuclear diatomics.
76
The molecular orbital diagrams for the second row homonuclear diatomics are
rather simple.
∗ ∗ ∗ See Supplement ∗ ∗∗
The supplement that follows this section contains examples for each of the second
row diatomics.
Heteronuclear diatomics are some what more complicated since there is a disparity
in the energy levels of the atomic orbitals for the separated atoms. This disparity
is not present for homonuclear diatomics.
The supplement that follows this section contains some examples of heteronuclear
diatomics.
Bond order
• One important property that can be predicted from the molecular orbital
diagrams is bond order.
77
10.4. The Complete Molecular Hamiltonian and Wavefunc-
tion
Likewise we have discussed molecular orbitals which are the electronic wavefunc-
tions.
Next semester we will discuss molecular rotations and just like for vibrations
and electronic transitions they are governed by the rotational Hamiltonian and
described by the rotational wavefunction.
78
11. An Aside: Light Scattering–Why
the Sky is Blue
This chapter addresses the topic of light scattering from two different perspectives.
• Classical electrodynamics
Since this is not a course on electrodynamics, we have to take several key results
from that theory on faith.
As usual we work under the electric dipole approximation and only focus on the
interaction of the electric field part of light with a dipole.
When the light interacts with the molecule an electric dipole is induced according
to
μ = αE, (11.1)
79
79
For light, the electric field part is
The polarizability also depends on the positions of nuclei to some degree. That
is, there is a vibrational (and rotational) contribution to the polarizability:
The first term corresponds to Rayleigh scattering where the scattered light is at
the same frequency as the incident light.
The second term corresponds to Stokes Raman scattering where the scattered
light is shifted to the red of the incident frequency.
80
The third term corresponds to anti-Stokes Raman scattering where the scattered
light is shifted to the blue of the incident frequency.
Classical electrodynamics can describe exactly how the oscillating electric dipole
emits electromagnetic radiation. It can be shown that the emitted intensity is
ω4 2
I= μ, (11.5)
3c3 0
where μ0 = α0 E0 for the case of Rayleigh scattering and μ0 = α1 E0 /2 for the case
of Raman scattering.
This quartic scattering dependence is, in fact, the reason why the sky is blue (from
the point of view of classical electrodynamics) and is called the Rayleigh scattering
law.
The spectrum of visible light from the sun incident on the outer atmosphere is
essentially flat as shown below.
81
We just learned that light scatters as it traverses the atmosphere according to
Rayleigh’s scattering law: I(λ) ∝ 1/λ4 .
The following figures illustrate why Rayleigh scattering implies that the sky is
blue.
11.2.1. Sunsets
We have focused on a blue sky, but red sunsets occur for the same reason–
Rayleigh scattering.
82
If we look directly at the sun during a sunset (or sunrise) it appears red because
most of the blue light has scattered in other directions.
This more pronounced at dawn or dusk since the light must traverse more of the
atmosphere at those times then at noonday at which time the sun appears yellow
in color.
We might expect that clouds should be highly colored since they consist of droplets
of water which scatter light very effectively.
83
The key difference between light scattering by clouds versus by the atmosphere is
the size of the scatterer.
The water droplets are much larger than the wavelenght of the light–quite the
opposite case as above.
In this limit an entirely different analysis is made–one does not have Rayleigh
scattering but instead has a process called Mie scattering.
84
Key Equations for Exam 2
Listed here are some of the key equations for Exam 2. This section should not
substitute for your studying of the rest of this material.
The equations listed here are out of context and it would help you very little to
memorize this section without understanding the context of these equations.
The equations are collected here simply for handy reference for you while working
the problem sets.
Equations
85
85
• The energy levels for the hydrogenic system are given by
Z 2R
En = − (11.9)
n2
where An is the normalization constant for the nth eigenfunction and Hn (y)
are the Hermite polynomials.
• The energy levels for the Morse oscillator are of the form
1 1
Evib,n = −De + hcω̃ e (n + ) − hcω̃e xe (n + )2 , (11.14)
2 2
hcω̃e
where ω̃ e xe together is the anharmonicity constant, with xe = 4De
.
86
• Bond order is defined as
1
BO = (# of bonding electrons − # of antibonding electrons) (11.15)
2
87
Part III
88
88
12. Rudiments of Statistical
Mechanics
When we study simple systems like a single molecule, we use a very detailed
theory, quantum mechanics.
However, most of the time in the real world we are dealing with macroscopic
systems, say, at least 100 million molecules.
It is simply impossible, even with the fastest computers, to write down and solve
the Schrödinger equation for those 100 million molecules, but often Avogadro’s
number of molecules.
So we need a less detailed theory called statistical mechanics, which allows one to
handle macroscopic sized systems without losing to much of the rigor.
89
89
• Microstate: The single particular state of one member of the ensemble given
by listing the individual states of each of the microscopic systems in the
macroscopic state.
S = k ln W (12.1)
Consider a random system that when measured can appear in one of two outcomes
(e.g., flipping coins).
One valuable piece of statistical information about system is knowing how many
different ways the system appears p times in, say, outcome 1 after N measure-
ments.
The number C(N, p) is also called the binomial coefficient because it gives the
coefficient for the pth order term in the expansion
X
N
N
(1 + x) = C(N, p)xp . (12.3)
p=0
90
This formula will allow us to derive a normalization constant so that we can obtain
the probability of obtaining p measurements of state 1.
X
N
N
(1 + 1) = C(N, p)(1)p (12.4)
p=0
X
N
2N = C(N, p).
p=0
For combinations we did not care what order the results of the measurements
occurred.
91
This is no problem for small numbers, but when we consider macroscopic systems
(1020 or so molecules) no calculator can handle factorials of such large numbers.
Sterlings Approximation:
• In place of evaluating factorials of large number one can use Sterling’s ap-
proximation to approximate the value of the factorial.
• Sterling’s approximation is
12.2. Fluctuations
The fluctuation about an average value for any observable property O is described
by the variance which is defined as
σ 2O ≡ O2 − Ō2 . (12.8)
92
For ensembles having large numbers of particles measured values of a property are
extremely sharply peaked about the average value.
93
13. The Boltzmann Distribution
Consider a isolated system of N molecules that has the set { i } energy levels
associated with it.
Since the system is isolated the total energy, E, and the total number of particles
will be constant.
The number of configurations for the system is then given by the number of
distinct permutations of the system
N!
W = . (13.3)
N1 !N2 ! · · ·
94
94
For the moment let us relax the isolation constraint.
Minimizing energy would be the case where all the particles are in the ground
state (say 1 ).
These two situations are contradictory and some compromise must be obtained.
We start by considering our original system–that being one with constant energy,
E and number of particles N
This is done using the mathematical technique of Lagrange multipliers (page 951
of your calc book).
We will not discuss this method in detail and consequently we cannot derive the
equilibrium configuration.
95
The pi represents the probability of finding the a randomly chosen particle or
system which has energy i . This is the Boltzmann distribution
gi e−β i
Pi = P −β
(13.5)
j gj e
j
Since we started with a isolated system, β and hence T are constants. A given
energy E will correspond to a unique temperature T.
We have already come across both the partition functions that we will use in this
class.
This partition function is not very useful to us so we will not discuss it further.
96
This was first encountered as the denominator of the Boltzmann distribution and
it is extremely important in statistical mechanics. (Note: the symbol Z is also
often used for the canonical partition function.)
We shall see in the next chapter that the partition function will provide a link
between the microscopic (quantum mechanics or classical mechanics) and the
macroscopic (thermodynamics).
There are other partition functions that are useful in different situations but we
will do nothing more than list two important ones here: i) the grand canonical
partition function and ii) the isothermal—isobaric partition function
In the following we give an argument which provides a relation between the par-
tition functions. It is not an exact relation as we derive it, but it is a very good
approximation for large numbers of particles.
97
The microcanonical partition function describes a system at fixed energy E. In
fact W is the number of available states of the ensemble at the particular energy
E. This is essentially the same as the degeneracy of the ensemble gE .
Conversely the canonical partition function describes a system with variable en-
ergy.
However, based on our previous discussion of fluctuations, even though the energy
of the ensemble is allowed to vary, the number of states with energy equal to the
average energy Ē is overwhelmingly large. That is, almost every state available
to the ensemble has energy Ē.
We will soon make use of the Boltmann’s equation in terms of the canonical
98
partition function:
so,
Ē
S = k ln Q + (13.11)
T
We ended the previous chapter by stating the total molecular energy (about the
center of mass) as
= ele + vib + rot . (13.12)
99
But, each Ej is made up of the contributions of all of the molecules:
a b c
Ej = l + m + n + ··· (13.16)
The total canonical partition function is the product of the molecular partition
functions.
For the case where the molecules are the same then all the qmol,i are the same:
qmol,i = qmol thus
qN
Q = mol . (13.18)
N!
This allows us to focus only on a single molecule:
X X
qmol = gi e−β i = gele,n gvib,v grot,J gtrans,m e−β ( ele,n + v ib ,v + ro t,J + tra(13.19)
n s,m )
i n,v,J,m
X X X X
gele,n e−β ele ,n
gvib,v e−β v ib ,v
grot,J e−β ro t,J
gtrans,m e−β tra n s,m
|n {z }| v {z }| J {z }|m {z }
qele qv ib qro t qtra n s
We now collect below the expression for each of these partition functions. You
will get the chance to derive each of these for your home work
100
The Translational Partition Function
V
qtrans = (13.20)
Λ3
where
h
Λ≡ √ (13.21)
2πmkT
is the thermal de Broglie wavelength.
However, the high temperature limit, which works for all gases (of linear molecules)
except H2 is
T
qrot ≈ (13.22)
σθr
2
where θr ≡ 8πh2 Ik (I is the moment of inertia) and σ is the so-called symmetry
number in which σ = 1 for unsymmetrical molecules and σ = 2 for symmetrical
molecules.
101
so
X
qele = gele,i e−β tele ,i
≈ gele,ground (13.24)
i
102
14. Statistical Thermodynamics
The partition function allows one to calculate ensemble averages which correspond
to macroscopically measurable properties such as internal energy, free energy,
entropy etc.
Ensemble averages
The ensemble average of any property is given by
1 X
Ō = Oi gi e−β i . (14.1)
Q i
Internal energy
One critical property of an ensemble is the average (internal) energy U.
1 X −β i
U ≡ Ē = i gi e . (14.2)
Q i
103
103
Now take the derivative of Q with respect to β gives
µ ¶ Ã " #!
∂Q ∂ X −β i X µ ∂e−β i ¶
= gi e = gi (14.4)
∂β n,V ∂β i i
∂β n,V
n,V
X
= − gi i e−β i
i
1 ∂y ∂ ln y
where we used the identity y ∂x
= ∂x
.
Pressure
Another important property is pressure.
104
we proceed as
µ −β i ¶ Ã !
1 X ∂e 1 ∂ X −β i
P = gi = gi e (14.10)
βQ i ∂V n,β βQ ∂V i
n,β
µ ¶ µ ¶
1 ∂Q 1 ∂ ln Q
= = .
βQ ∂V n,β β ∂V n,β
Entropy
We have already obtained the expression for entropy. It is
U
S = + k ln Q (14.11)
T µ ¶
∂ ln Q
= −kβ + k ln Q
∂β n,V
105
Helmholtz Free Energy
Free energy is the energy contained in the system which is available to do work.
That is, it is the energy of the system minus the energy that is “tied-up” in the
random (unusable) thermal motion of the particle in the system: A ≡ U − T S
Free energy is probably the key concept in thermodynamics and so we will discuss
it in much greater detail later. We will make the distinction between the Helmholtz
free energy and the more familiar Gibb’s free energy (G) later as well.
The Helmholtz free energy has the most direct relation to the partition function
as can be seen from
µ ¶ µ ¶
∂ ln Q ∂ ln Q
A ≡ U − TS = − + kT β − kT ln Q (14.12)
∂β n,V ∂β n,V
= −kT ln Q
Any thermodynamic property can now be obtained from the above functions as
we shall see in the following chapters.
106
15. Work
∗ ∗ ∗ See Handout ∗ ∗∗
107
107
3. The reciprocal rule: µ ¶ µ ¶
∂z ∂x
=1 (15.3)
∂x y ∂z y
5. Finally µ ¶ µ ¶ µ ¶ µ ¶
∂z ∂z ∂z ∂y
= + (15.5)
∂x u ∂x y ∂y x ∂x u
15.2. Definitions
Note that the distinction between the system and the environment is arbitrary
and is chosen as a matter of convenience.
Isolated system: A system that cannot exchange matter or energy with its envi-
ronment.
Closed system: A system that cannot exchange matter with its environment but
may exchange energy.
108
Open system: A system that may exchange matter and energy with its environ-
ment.
Adiabatic system: A closed system that also can not exchange heat energy with
its environment.
A system may exchange energy with its environment or another system in the
form of work or heat.
• Heat is exchanged if only internal parameters are changed during the process.
109
Convention
Work, w, is positive (w > 0) if work is done on the system.
In physics you learned that an infinitesimal change in work is given by the product
of force, F , times and infinitesimal change in position, dx:
dw = F dx. (15.7)
Note that the generalized force need not have units of force (e.g., Newtons) and
the generalized displacement need not have units of position (e.g., meters), but
the product of the two must have units of energy (e.g., Joules).
dw = Ada, (15.8)
or more generally as
X
dw = Ai dai (15.9)
i
110
if more than one set of parameters change.
The following table gives some examples of generalized forces and displacements
Generalized Force, A Generalized Displacement, a Contribution to dw
Pressure, −P Volume, dV −P dV
Stress, σ Strain, dε σdε
Surface tension, γ Surface area, dA γdA
Voltage, E Charge, dQ EdQ
Magnetic Field, H Magnetization, dM HdM
Chemical Potential, μ Moles, dn μdn
Gravity, mg Height, dh mgdh
15.3.2. P V work
dw = −P dV, (15.10)
Expanding Gases
Consider the work done by a gas expanding in piston from volume V1 to V2 against
some constant external pressure P = Pex (see figure)
111
The force exerted on a gas by a piston is equal to the external pressure times the
area of the piston: F = Pex A ⇒ Pex = F/A.
Rx
Recall from physics that work is the (path) integral over force: w = − x12 F dx.
This can be manipulated as
Z x2 Z x2 Z V2
F
w=− F dx = − Adx = − Pex dV (15.11)
x1 A |{z}
x1 |{z} V1
dV
Pex
112
16. Maximum Work and Reversible
changes
Now that we have learned about PV work we will consider the situation where
the system does the maximum amount of work possible.
In the figure Z V2
wA = − Patm dV = −Patm (V2 − V1 ) (16.1)
V1
113
113
and
wB = w1 + w2 , (16.2)
where Z Vi
w1 = − Patm+2W dV = −Patm+2W (Vi − V1 ) (16.3)
V1
and Z V2
w2 = − Patm dV = −Patm (V2 − Vi ) (16.4)
Vi
This is the limiting case of path B in the previous figure. Thus wrev is the maxi-
mum possible work that can be done in an expansion. wrev = wmax .
114
16.2. Heat Capacity
The heat capacity also depends on the conditions during the temperature change,
¡ dq ¢ ¡ dq ¢
e.g., CV (T ) = dT V
and CP (T ) = dT P
are not the same
115
16.3. Equations of State
The macroscopic properties of matter are related to one another via a phenom-
enological equation of state.
The state of a pure, homogeneous material (in the absence of external fields) is
given by the values of any two intensive properties.
(More complicated systems require more than two independent variables, but
behave in the same way as the more simple pure system, so we will focus our
development of thermodynamics on simple systems.)
P V = nRT , (16.10)
where R is the gas constant (8.315 J K−1 mol−1 ) and n is the number of moles.
The ideal gas equation of state can be expressed in terms of intensive variables
only
P Vm = RT , (16.11)
V
where Vm = n
.
m
The equation of state can also be expressed in terms of density ρ = V
(and molar
mass m/n)
mP MP
ρ= = . (16.12)
nRT RT
116
16.3.2. Example 2: The van der Waals Equation of State
nRT n2 a
P = − 2. (16.13)
V − nb V
The parameter a attempts to account for the attractive forces among the particles
The parameter b attempts to account for the repulsive forces among the particles
117
In term of intensive variables
RT a
P = − 2. (16.14)
Vm − b Vm
The van der Waals equation of state is not the only one that has been proposed.
Some other equations of state are
• Berthelot
nRT n2 a RT a
P = − 2
= − (16.15)
V − nb T V Vm − b T Vm2
• Dieterici an a
nRT e− RT V RT e− RT Vm
P = = (16.16)
V − nb Vm − b
• Redlich-Kwang
nRT n2 a RT a
P = −√ = −√ (16.17)
V − nb T V (V − nb) Vm − b T Vm (Vm − b)
118
17. The Zeroth and First Laws of
Thermodynamics
Over the course of the next two lectures we will discuss the four core laws of
thermodyanmics.
Today we will cover the zeroth and first laws, which deal with temperature and
total energy respectively.
Next time we will cover the second and third laws which both deal with entropy.
Temperature scales
• Kelvin: An absolute temperature scale based on the ideal gas law. The
temperature at which (for fixed V and n) the pressure is zero is defined as
T =0K
119
119
Standard conditions
Adiabatic wall: A wall the does not allow heat to flow through it.
Thermal equilibrium: If two systems are in contact along a diathermic wall and
no heat flows across the wall, then the systems are in thermal equilibrium.
• Mathematical statement:
120
17.2. The First Law of Thermodynamics
Definitions:
For characterizing the change in energy of a system, one is concerned with the
work done on the system (w) and the heat supplied to the system (q). The energy
of a system is called the internal energy (U) of the system.
• Mathematical statement:
4U = q + w (17.2)
or in differential form
dU = dq + dw (17.3)
So for a system where all the work is P V work the first law becomes
Z V2
4U = q − Pex dV (17.4)
V1
121
in differential form this is
dU = dq − Pex dV (17.5)
Although U can be expressed as a function of any two state variables, the most
convenient at this time are V and T. U → U(T, V ).
So, µ¶ µ ¶
∂U ∂U dq
dT = dq =⇒ = = CV (17.8)
∂T V ∂T V dT
¡ ¢
Hence the slope ∂U
∂T V
is the heat capacity.
¡ ∂U ¢
The other slope, ∂V T
, is called the internal pressure (it has no standard symbol).
122
so the useful relation becomes
µ ¶
∂U nR nRT nRT n2 a
= T −P = − + 2
∂V T V − nb V − nb V − nb V
2
na
= + 2 (17.11)
V
123
18. The Second and Third Laws of
Thermodynamics
Furthermore we derived the simple relation between the Helmholtz free energy
and the canonical partition function as A = −kT ln Q.
Hence,
U A 1
S= − = (U − A). (18.2)
T T T
Since U, A, and T are state functions, S is also a state function .
So we may write
1
dS = (dU − dA) (18.3)
T
124
124
for an isothermal process.
Recall the definition of Helmholtz free energy–the energy of the system available
to do work.
We learned previously that the maximum amount of work one can extract from
the system is the work done during a reversible process. Hence dA = dwrev .
125
Since U, S, T, P, and V are state functions, dU = T dS − P dV holds for any
process, but in general, T dS is not heat and −P dV is not work. (see figure)
T dS = dq + (P − Pex ) dV
• Case ii) P > Pex then (spontaneous) dV is positive so (P −Pex )dV is positive.
126
18.1.1. Statements of the Second Law
Unlike the first law, the second law has a number of equivalent statements
dU = dq + dw = dq − Pex dV (18.6)
From our earlier discussion of heat capacity dq = CV dT (CV since constant vol-
ume). So,
dU = CV dT (18.7)
127
A very similar derivation can be done for a reversible change at constant pressure
(we can not do it quite yet) to yield
Z T2
CP
4S = dT (18.9)
T1 T
Verbal statement
The third law of thermodynamics permits the absolute measurement of entropy.
now let T1 → 0 Z T2
CP
4S = S2 − S0 = dT (18.11)
0 T
Hence the mathematical statement of the third law is
Z T2
CP
S(T2 ) = dT + S0 (18.12)
0 T
From a macroscopic point of view S0 is arbitrary. However, a microscopic point of
view suggests S0 = 0 for perfect crystals of atoms or of totally symmetric molecules
(e.g., Ar, O2 etc.). S0 6= 0 for imperfect crystals and crystals of asymmetric
molecules (e.g., CO).
CP
For S0 to have significance T
must be finite (not infinite) as T → 0. Thus CP → 0.
128
dq dT
But CP = dT
→ 0 implies dq
→ ∞.
In view of what we have learned about fluctuations, the ever present random
fluctuations in energy provide the infinitesimal amount of heat and so you can
never reach absolute zero corresponding to an average energy of zero.
Heat capacity data only goes down so far. So one needs a theoretical extrapolation
down to T = 0. (Debye)
129
The molar entropy is
Z T∗ ∗ Z T∗
∗ CP C =aT 3 CP m
Sm (T ) = dT P m= T 2 dT (18.13)
0 T T ∗3 0
¯T ∗
CP∗ m T 3 ¯¯ CP∗ m
= = .
T ∗3 3 ¯ 0 3
For example, if we see a picture of your PChem book in mint condition and we see
a picture of your PChem book all battered and beaten. We know which picture
was taken first.
The interesting thing is that each molecule in a macroscopic system obeys time
invariant dynamics. Both Newton’s laws and Quantum dynamics (next semester)
are the same if you replace t with −t.
Yet, the behavior of the macrosystem definitely changes if you replace t with −t.
Thus the simple fact that you have an enormous number of particles induces a
perceived asymmetry in time.
130
Key Equations for Exam 3
Listed here are some of the key equations for Exam 3. This section should not
substitute for your studying of the rest of this material.
The equations listed here are out of context and it would help you very little to
memorize this section without understanding the context of these equations.
The equations are collected here simply for handy reference for you while working
the problem sets.
Equations
131
131
• The relation between the partition function and the molecular partition
function is
qN
Q = mol . (18.17)
N!
• The Translational Partition Function
V
qtrans = 3 (18.18)
Λ
where
h
Λ≡ √ (18.19)
2πmkT
is the thermal de Broglie wavelength.
1
qvib = . (18.21)
2 sinh 12 β~ω
• The ensemble average of any property is given by
1 X
Ō = Oi gi e−β i . (18.22)
Q i
• The relations between the canonical partition function and the thermody-
namics variables are
Helmholtz Free Energy A = −kT³ln Q´ ³ ´
∂Q ∂ ln Q
Internal energy U = − Q1 ∂β
=− ∂β
³ ´
n,V n,V
∂ ln Q
Entropy S = −kβ ∂β + k ln Q
n,V
¡ ∂Q ¢ ¡ ∂ ln Q ¢
Pressure P = βQ ∂V n,β = β1
1
∂V n,β
132
• P V work is
dw = −P dV. (18.23)
• Heat capacity:
dq = C(t)dT. (18.24)
4U = q + w, (18.25)
Also,
dU = T dS − P dV. (18.27)
133
Part IV
Basics of Thermodynamics
134
134
19. Auxillary Functions and Maxwell
Relations
Consequently, the concept of equilibrium plays a key role in much of what we will
discuss for the remainder of the year.
The equilibrium constant for a thermodynamic process, K, (which you are familiar
with from general chemistry) serves are a common point which connects thermo-
dynamics, electrochemistry, and kinetics–topics we will encounter throughout
the year.
As was the case in quantum mechanics, here too is energy the key property with
which to work.
So far we have encountered two state functions which characterize the energy of a
macroscopic system–the internal energy and, briefly the Helmholtz free energy.
135
135
From the first law as stated as
dU = T dS − P dV (19.1)
we say that the natural (most convenient) variables for the equation of state for
U are S and V . This is U = U(S, V )
Unfortunately S can not be directly measured and most often P is a more conve-
nient variable than V
Because of this fact, it is handy to define state functions which have different pairs
of natural variables, so that no mater what situation arises we have convenient
equations of state to work with.
The other pairs of natural variables being (S and P ), (T and V ) and (T and P )
19.2. Enthalpy
136
Now formally
dH = dU + d(P V ) = dU + P dV + V dP, (19.2)
but dU = T dS − P dV, so
/ + P dV/ + V dP
dH = T dS − P dV (19.3)
= T dS + V dP.
Enthalpy is the total energy of the system minus the pressure volume energy. So
a change in enthalpy is the change in internal energy adjusted for the P V work
done. If the process occurs at constant pressure then the enthalpy change is the
heat given off or taken in.
For example, consider an reversibly expanding gas under constant pressure (dP =
0) and adiabatic (dq = 0) conditions.
The system does work during the expansion; in doing so it must lose energy. Since
the process is adiabatic no heat energy can flow in to compensate for the work
done and the gas cools.
The total internal energy decreases. The enthalpy of the system on the other hand
does not change–it is the internal energy adjusted by an amount of energy equal
to the P V work done by the system. As Freshmen we learn this as 4H = qp .
137
Let us try the definition A ≡ U − T S.
Formally
dA = dU − d(T S) = dU − T dS − SdT, (19.4)
but dU = T dS − P dV, so
/ − P dV − T dS
dA = T dS / − SdT (19.5)
= −P dV − SdT.
Hence Helmholtz free energy does indeed have the desired natural variables.
As we have said before Helmholtz free energy is the energy of the system which is
available to do work–It is the internal energy minus that energy which is “used
up” by the random thermal motion of the molecules.
Now formally
dG = dH + d(T S) = dH − T dS − SdT, (19.6)
but from above dH = T dS + V dP, so
/ + V dP − T dS
dG = T dS / − SdT (19.7)
= V dP − SdT.
Hence Gibbs free energy does indeed have the desired natural variables.
138
19.4.1. Heuristic definition:
Gibbs free energy is the energy of the system which is available to do non P V
work–It is the internal minus both that energy which is “used up” by the random
thermal motion of the molecules and used up in doing the P V work.
dH = T dS + V dP (19.8)
dH = T dS (19.9)
dH = dq
but
dq = CP dT (19.10)
The constant pressure heat capcity can then be expressed in terms of enthalpy as
µ ¶
∂H
CP = . (19.11)
∂T P
So, µ ¶ µ ¶ µ ¶
∂ (U + P V ) ∂U ∂V
CP = = +P (19.12)
∂T P ∂T P ∂T P
¡ ¢ ¡ ∂U ¢
note ∂U
∂T P
is not CV we need ∂T V
. Use an identity of partial derivatives
µ ¶ µ ¶ µ ¶ µ ¶
∂U ∂U ∂U ∂V
= + (19.13)
∂T P ∂T V ∂V T ∂T P
139
thus
µ ¶ µ ¶ µ ¶ µ ¶
∂U ∂U ∂V ∂V
CP = + +P (19.14)
∂T V ∂V T ∂T P ∂T P
µ ¶ ∙µ ¶ ¸
∂V ∂U
= CV + +P .
∂T P ∂V T
¡ ∂U ¢ ¡ ∂P ¢
Recall the expression for internal pressure ∂V T
= T ∂T V
− P . Then
µ ¶ ∙ µ ¶ ¸
∂V ∂P
CP = CV + T / + P/
−P (19.15)
∂T P ∂T V
Finally µ ¶ µ ¶
∂V ∂P
CP = CV + T (19.16)
∂T P ∂T V
• H = U + PV
140
• A = U − TS
• G = H − TS
¡ ∂U ¢ ¡ ∂H ¢
• CV = ∂T V
, CP = ∂T P
We will get plenty of practice with derivations based on these equations and on
the properties of partial derivatives. (See handout and Homework)
141
20. Chemical Potential
For chemistry it is most often more convenient to use Gibbs free energy
142
142
For constant T and P = Pex , (dG)T,P = dq − T dS
Again from the second law, T dS ≥ dq for a spontaneous process, (dG)T,P ≤ 0 for
a spontaneous process.
Note free energy provides no information about how fast a process proceeds to
equilibrium.
dA = dU − T dS − SdT (20.3)
and
dG = dH − T dS − SdT. (20.4)
Expressing dU and dH generally as dU = T dS − P dV and dH = T dS + V dP
(remember that in general T dS cannot be identified with dq and P dV cannot be
identified with −w).
dA = −SdT − P dV (20.5)
and
dG = −SdT + V dP (20.6)
143
These expressions are quite general, but i) only P V work and ii) closed systems.
dA = dq + dw − T dS − SdT. (20.7)
dG = dq + dw + P dV + V dP − T dS − SdT. (20.8)
0 0
(dG)T,P = dwmax =⇒ (4G)T,P = wmax (20.10)
So, as stated earlier, the Gibbs free energy is the energy of the system available
to do non-P V work.
144
Extensive properties depend on the amount of “stuff”
For example A(T, V ) now becomes A(T, V, n) and the total differential becomes
µ ¶ µ ¶ µ ¶
∂A ∂A ∂A
dA(T, V, n) = dT + dV + dn (20.11)
∂T V,n ∂V T,n ∂n V,T
¡ ∂A ¢
Let’s focus on the slope ∂n V,T
.
What about the relation of the chemical potential to Gibbs’ free energy?
G = H − TS = U
| −
{zT S} + P V = A + P V so,
=A
dG = dA + P dV + V dP (20.13)
/ dV/ + P/ dV/ + V dP + μdn
= −SdT − P
= −SdT + V dP + μdn,
but from µ ¶ µ ¶ µ ¶
∂G ∂G ∂G
dG = dT + dP + dn (20.14)
∂T P,n ∂P T,n ∂n P,T
145
we see that µ ¶
∂G
μ= . (20.15)
∂n P,T
So, μ is also a measure of the change in Gibbs free energy of a system (at constant
T and P ) with the change in the amount of material and it still has the same
physical meaning.
The Gibbs free energy per mole (Gm ) for a pure substance is equal to the chemical
potential. (Gm = μ)
To account for this one must introduce the concept of activity and the activity
coefficient.
The activity coefficient has a more convenient definition which is that it is the
measure of how a particular real system deviates from some reference system
which is usually taken to be ideal.
where g(ζ) is any reference function (e.g., pressure, mole fraction, concentration
etc.), and ζ ª is the value of ζ at the reference state.
146
This implicit definition is awkward so for convenience one defines the activity
coefficient as the argument of the above limit,
ai
γi ≡ (20.17)
g(ζ)
Because of this it is always necessary to specify a reference state to which our real
state can be compared.
The choice of this state is completely up to us, but it is often the case that the
reference state is chosen to be some ideal state.
For example, if we are talking about a gas we will mostly likely choose the ideal
gas law in terms of pressure (P = nRT /V ) as our reference function and the
reference state being when P = 0 since we know all gases behave ideally in the
limit of zero pressure.
Let us consider the activity of a real gas for the above reference function and
reference state. Note: the activity of gases as referenced to pressure has the
special name fugacity (fugacity is a special case of activity).
147
Our reference function is very simple: g(ζ) = ζ = P , so
a
γ= ⇒ a = γP. (20.19)
P
Thus the activity of our real gas is given by the activity coefficient times the
pressure of an ideal gas under the same conditions.
One cannot measure absolute chemical potentials, only relative potentials can be
measured. By convention we chose a standard state and measure relative to that
state.
The deviation of the chemical potential at the state of interest versus at the
reference state is determined by the activity at the current state (the activity at
the reference state is unity by definition).
μi − μª
i = RT ln ai . (20.20)
Rather than referencing to the standard state one can also reference to any con-
venient “ideal” state. This ideal state is in turn referenced to the standard state.
For the state of interest
μi = μªi + RT ln ai (20.21)
μid ª id ª id id
i = μi + RT ln ai ⇒ μi = μi − RT ln ai . (20.22)
148
Thus,
μi = μid id
i − RT ln ai + RT ln ai (20.23)
μi − μid
i = +RT ln ai − RT ln aid
i
ai
= RT ln id
ai
Example: Real and ideal gases at constant temperature, but any pressure.
Starting from the begining
=0
z}|{
id
dμ = dGm = −Sm dT + Vm dP (20.24)
dμid = Vm dP
RT
dμid = dP.
P
Now we integrate from the reference state to the current state of interest
Z Z
id RT
dμ = dP. (20.25)
μª Pª P
This gives
P
μid − μª = RT ln . (20.26)
Pª
The usual standard state is the ideal gas at P ª = 1, so
μid = μª + RT ln P. (20.27)
μ = μª + RT ln a. (20.28)
For gases activity is usually called fugacity and given the symbol f , so a = f for
real gasses. Thus
μ = μª + RT ln f. (20.29)
149
Lets say that instead of referencing to the ideal gas at P = 1, we want to reference
to the ideal gas at the current pressure P.
μ = μid − RT ln P + RT ln f
f
μ = μid + RT ln .
P
So at sea level
=0
z }| {
id
μ (0) = μ + RT ln 1 = μª
ª
(20.31)
and at elevation h
μid (h) = μª + RT ln Ph (20.32)
The gas fields the gravitational force which gives it a potential energy per mole
of Mgh at height h. We add this energy per mole term to the chemical potential
(which is free energy per mole) thus at equilibrium
The last line is the barometric equation and it shows that pressure is exponentially
decreasing function of altitude.
150
21. Equilibrium
μA = μB (21.1)
Now,
μA = μª
A + RT ln aA (21.2)
and
μB = μª
B + RT ln aB
μª ª
A + RT ln aA = μB + RT ln aB (21.3)
−4μª = μª ª
A − μB = RT ln aB − RT ln aA
aB
−4μª = RT ln
aA
Since chemical potential is free energy per mole, if we multiply the above by n
moles we have
aB
−4Gª = nRT ln
aA
as a consequence of the equilibrium condition.
The quantity aaBA defines the equilibrium constant, Ka , for this process.
151
151
Say the system A → B is not in equilibrium then we can not write
μA = μB
μª ª
A + RT ln aA + 4μ = μB + RT ln aB (21.5)
4μ = μª ª
B − μA + RT ln aB − +RT ln aA
aB
4μ = 4μª + RT ln .
aA
Again multiplying by n gives
aB
4G = 4Gª + nRT ln .
aA
If the 4G < 0 then the transition A → B proceeds spontaneously as written.
aA + bB cC + dD. (21.6)
aμª ª ª ª
A + aRT ln aA + bμB + bRT ln aB = cμC + cRT ln aC + dμD + dRT ln aD (21.8)
Rearranging gives
≡−4rx n Gª
z }| { acC adD
aμª
A + bμª
B − cμª
C − dμª
D = RT ln (21.9)
aaA abB
152
the equilibrium constant is
acC adD
Ka = a b =⇒ 4Gª = −RT ln Ka (21.10)
aA aB
Note: n is absent in the above since the molar values are implied by the stoi-
chiometry.
[C]c [D]d
KC0 = , (21.11)
[A]a [B]b
which is related to Ka by µ ¶
γ cC γ dD
Ka = KC0 . (21.12)
γ aA γ bB
If the reactants are solutes then as the solution is diluted all the activity coefficients
go to unity and KC0 → Ka .
153
The equilibrium equation is
Aα Aβ (21.13)
4Gα→β = 0 = 4Gª
α→β − nRT ln Ka , (21.14)
where, 4Gª ª ª
α→β ≡ Gβ −Gα . The equilibrium constant for this process has a special
β/α
name; it is called the partition coefficient, P β/α ≡ Kpart , for species A in the α—β
mixture.
aβ 4G ª
α→β
β/α − nRT
P = A
α
= e . (21.15)
aA
154
For most drugs
o/w
0 < Ppart < 4 (21.17)
Factors other than the partition coefficient influence the drug delivery choice. For
example, can the drug handle the acidic environment of the stomach?
155
22. Chemical Reactions
• Example
156
156
22.1.1. Heats of Formation
157
22.2. Reversible reactions
Recall the requirement for a spontaneous change: 4G < 0 for constant T and P.
X
4rxn G = G(products) − G(reactants) = ν i μi , (22.3)
i
μi = μª
i + RT ln ai . (22.4)
So,
4rx n Gª
zX}| { X
4rxn G = ν i μª
i + RT ν i ln ai . (22.5)
i i
• Note that the activity of any pure solid or liquid is for all practical purposes
equal to 1.
158
Pi Xi P
• For ideal gases, ai = Pª
= Pª
(P ª = 1 bar) This leads to the sometimes
useful relation
PCc PDd (P ª aC )c (P ª aD )d ¡ ª ¢c+d−a−b
KP = = = Ka P , (22.8)
PAa PBb (P ª aA )a (P ª aB )b
S
νi
or more generally KP = Ka (P ª ) i
.
Starting with
³ G =´H − T S or G/T = H/T − S.
From this ∂(G/T )
∂(1/T )
= H.
P
Applying this to
4rxn Gª 4rxn H ª
= − 4rxn S (22.10)
T T
gives µ ¶
∂(4rxn Gª /T )
= 4rxn H ª (22.11)
∂(1/T ) P
ª
Using 4rxn G = −RT ln Ka , we get
µ ¶
∂ ln Ka ind. d ln Ka 4rxn H ª
= =− (22.12)
∂(1/T ) P of P d(1/T ) R
d dT d d
or (using d(1/T )
= d(1/T ) dT
= −T 2 dT )
d ln Ka 4rxn H ª
= (22.13)
dT RT 2
Integration gives
Z T2 ª
1 4rxn Hm
ln Ka (T2 ) = ln Ka (T1 ) + (22.14)
R T1 T2
For a reasonably small range T2 − T1 this is well approximated by
ª
µ ¶
4rxn Hm 1 1
ln Ka (T2 ) = ln Ka (T1 ) − − (22.15)
R T2 T1
159
22.4. Extent of Reaction
There are other equilibrium “constants” that are used in the literature.
• From Pj = Xj P , KX = KP P −4υg
V
¡ RT ¢−4υg
• From nj = Pj RT (ideal gas approximation), Kn = KP V
nj Pj
• From concentration Cj = V
= RT
, KC = KP (RT )−4υg
Equilibrium “constants”
“constants” expression relation to Ka situation used
activity(products)
Ka activity(reactants)
– when an exact answer is needed
partial pressure(products) Ka
KP partial pressure(reactants) −4υ g gas reactions
µ Kγ P ª ¶
mole fraction(products) Ka −4υ g
KX mole fraction(reactants) −4υ g P when eq. P is known
Kγ P ª
µ ¶
moles(products) Ka
¡ RT ¢−4υg
Kn moles(reactants) −4υ g V
when V is known and constant
Kγ P ª
µ ¶
KC concentration(products)
concentration(reactants)
Ka
−4υ g (RT )−4υg when concentration known
Kγ P ª
160
23. Ionics
To understand these processes we must know something about how ions behave
in solution.
where v+ (v− ) is the number of cations (anions) and z+ (z− ) is the charge on the
cation (anion).
The chemical potential for the salt may be written in terms of the chemical po-
tential for each of the ions:
μsalt = v+ μ+ + v− μ− (23.2)
μj − μª
j
ln aj = , j = + or − (23.3)
RT
and
μsalt − μª
salt
ln asalt = . (23.4)
RT
161
161
Substituting the expression for μsalt into this gives
v+ μ+ − v− μ− + v+ μª ª
+ − v− μ−
ln asalt = (23.5)
RT
v+ μ+ − v+ μª
+ v− μ− − v− μª
−
= +
| RT
{z } | RT
{z }
v+ ln a+ v− ln a−
So,
ln asalt = v+ ln a+ + v− ln a− (23.6)
or, alternatively,
asalt = av+ av− (23.7)
The activity coefficients for ionic solutions can also be defined via
a+ = γ + m+ , a− = γ − m− , (23.10)
where m+ = v+ m and m− = v− m.
162
The quantities a+ , a− , γ + and γ − cannot be measured individually.
One can use the colligative properties to measure the ionic activity coefficients.
θ = vφKf m. (23.13)
163
where
µ ¶1/2
e3 2πρ• L
α= , (23.17)
(εkT )3/2 1000
8πLe2 ρ•
B= , (23.18)
1000εkT
a0 is the radius of closest approach, e is the charge on the electron, ρ• is the
density of the pure solvent, ε is the dielectric constant for the pure solvent and L
is Avogadro’s number.
One important approximation to this equation is to neglect the B term to get the
Debye—Hukel limiting Law (DHLL):
√
ln γ ± = −α |z+ z− | I. (23.19)
This gives the dependence of ln γ ± for dilute solutions (m → 0). It is seen that
√
the DHLL correctly predicts the m dependence of ln γ ± , which is observed ex-
P
perimentally (recall I = 12 i zi2 mi ).
164
(Electrical) work, w, is required to move a change through a potential (or voltage),
ε:
w = −εQ (23.22)
p = −εI (23.23)
165
The total current passing through an ionic solution is determined by the sum of
the current carried by the cations and by the anions
I = I+ + I− (23.24)
Now
dQi dNi
Ii = = |zi | e , (23.25)
dt dt
where i = +, −.
For uniform ion velocity (vi ) the number of ions arriving at the electrode during
any given time interval 4t is
Ni dNi Ni
4Ni = Avi 4t =⇒ = Avi (23.26)
V dt V
so
Ni
Ii = |zi | e Avi (23.27)
V
Recall Coulomb’s law
Fi = zi eE, (in vacuum) (23.28)
dε
where E is the electric field, E = dx
.
Also recall Newton’s law
dvi
Fi = mai = m = zi eE. (23.29)
dt
The moving ions experience a viscous drag f that is proportional to their velocities.
So the total force on the ions is a sum of the Coulomb force and the viscous drag
The ions quickly reach terminal velocity, i.e., the viscous drag equals the Coulomb
force. Hence Fi = 0.
zi eE
zi eE = f vi =⇒ vi = . (23.31)
f
The drag f has three basic origins.
166
1. Stoke’s Law type force
2. Electrophoretic effect.
3. Relaxation effects
167
A more fundamental quantity than ion velocity is the ion mobility, ui which is the
ion’s velocity per field,
vi
ui = . (23.32)
E
For the case for parallel plate capacitors E = εl , where l is the separation of the
plates. So,
vi l
ui = . (23.33)
ε
Here the current carried by ion i is
Ni ui ε
Ii = |zi | e A . (23.34)
V l
Suppose a salt has a degree of dissociation α (α = 1 for strong electrolytes) to
produce ν + cations and ν − anions, then each mole of salt gives: N+ = αν + Ln
and N− = αν − Ln.
168
24. Thermodynamics of Solvation
The way to investigate the ion—solvent interaction upon solvation from a thermo-
dynamics point of view is to consider the change in the properties of the ion in a
vacuum versus the ion in solution.
Since Gibbs free energy corresponds to non-P V work, 4Gv→s can be determined
by calculating the reversible work done in transferring an ion into the bulk of the
solvent.
169
169
24.1. The Born Model
The Born model is a simple solvation model in which the ions are taken to be
charged spheres and the solvent is take to be a continuum with dielectric constant
εs
170
4Gv→s for the Born model is obtained by considering the following contribution
to the work of ion transfer from the vacuum state to the solvated state (see figure)
• Begin with the state in which the charged sphere (the ion) is in a vacuum.
• Assume the uncharged sphere can pass from the (neutral) vacuum to the
neutral solvent without doing any work, wtr = 0. (This is an approximation).
• Determine the work, wch , done in charging the sphere which is now in the
solvent.
171
So,
4Gv→s = wdis + wtr + wch = wdis + wch (24.1)
The work done is discharging is some what complicated since as one removes the
charge the work done in removing more charge changes according to the amount
of charge currently on the sphere.
172
This is expressed mathematically as
Z 0Z ∞
σ
wdis = 2
drdσ (24.2)
ze ri 4π 0 r
Z 0
σ
= dσ
ze 4π 0 ri
(ze)2
= − ,
8π 0 ri
where z is the oxidation state of the ion, e is the charge of the electron, ri is the
radius of the sphere (ion) and 0 is the permittivity of free space.
So,
(ze)2
wch = + (24.3)
8π 0 εs ri
(ze)2 (ze)2
4Gv→s = − + (24.4)
8π 0 ri 8π 0 εs ri
µ ¶
(ze)2 1
= −1
8π 0 ri εs
173
The dielectric constant of any solvent is always greater than unity so ε1s − 1 is
always negative hence 4Gv→s < 0. Thus ions always exist more stably in solution
than in a vacuum.
We can quickly generalize the Born model to describe ion transfer between phases
in a solution of two immiscible phases
Since Gibbs free energy is a state function we can write the change in free energy
for transfer of an ion form the β phase to the α phase as
=−4Gv →β
z }| {
4Gβ→α = 4Gβ→v + 4Gv→α (24.6)
µ ¶ µ ¶
N (ze)2 1 N (ze)2 1
= − −1 + −1
8π 0 ri εβ 8π 0 ri εα
µ ¶
N (ze)2 1 1
= −
8π 0 ri εα εβ
We can now write the partition coefficient for the Born model as
−4Gª L(ze)2 1
α/β β→α − 8πr − ε1
i 0 RT εα
Pi =e nRT =e β
(24.7)
174
From µ ¶ µ ¶
∂G ∂4Gv→s
= −S ⇒ = −4Sv→s , (24.8)
∂T P ∂T P
we find entropy to be
" µ ¶#
∂ N (ze)2 1
4Sv→s =− −1 . (24.9)
∂T 8π 0 ri εs
The only variable in the above equation that has a temperature dependence is the
dielectric constant of the solvent so,
µ ¶
N (ze)2 ∂ 1 N (ze)2 ∂εs
4Sv→s = − = . (24.10)
8π 0 ri ∂T εs 8π 0 ri ε2s ∂T
Unfortunately however, the Born model does not make quantitatively correct pre-
dictions in many cases.
We simply list here several phenomena that more sophisticated theories of solva-
tion must consider
175
1. The solvophobic effect: a cavity must form in the solvent to accommodate
the ion.
2. Changes in solvent structure: the local environment of the ion has a different
arrangement of solvent molecules than that of the bulk solvent, so the initial
structure of the solvent must breakdown and the new structure must form.
176
25. Key Equations for Exam 4
Listed here are some of the key equations for Exam 4. This section should not
substitute for your studying of the rest of this material.
The equations listed here are out of context and it would help you very little to
memorize this section without understanding the context of these equations.
The equations are collected here simply for handy reference for you while working
the problem sets.
Equations
H = U + PV dH = T dS + V dP
A = U − TS dA = −SdT − P dV
G = H − TS dG = −SdT + V dP
μi = μª
i + RT ln ai (25.1)
4G = 4Gª + RT ln Q. (25.2)
177
177
At equilibrium 4G = 0 and
• The ratio of the current carried by the cation versus the anion in terms of
ion mobility is
I+ u+
= (25.6)
I− u−
• The chemical potential equation
μi = μª
i + RT ln ai (25.7)
4G = 4Gª + RT ln Q. (25.8)
At equilibrium 4G = 0 and
178
Chemistry 352: Physical
Chemistry II
179
179
Part V
180
180
26. Particle in a 3D Box
In particular we will look at the particle in a box in more than one dimension.
Recall that the important ideas from the 1D particle in a box problem were
181
181
Now, in region I and III, where the potential is infinite, the particle can never
exist so, ψ must equal zero in these regions.
−~2 d2 ψ(x)
Ĥψ = Eψ =⇒ = Eψ, (26.2)
2m dx2
The general solution of this differential equation is
Now ψ must be continuous for all x. Therefore it must satisfy the boundary
conditions (b.c.): ψ(0) = 0 and ψ(a) = 0.
From the ψ(0) = 0 b.c. we see that the constant B must be zero because
cos kx|x=0 = 1.
So we are left with ψ(x) = A sin kx for our wavefunction.
182
The second b.c., ψ(a) = 0, places certain restrictions on k.
In particular,
nπ
,
kn = n = 1, 2, 3, · · · . (26.4)
a
The values of k are quantized. So, now we have
nπx
ψn (x) = A sin . (26.5)
a
Thus our normalized wavefunctions for a particle in a box are (in region II)
r
2 nπx
ψ n (x) = sin . (26.7)
a a
183
Now the Schrödinger equation is
−~2 2
Ĥψ = Eψ ⇒ ∇ ψ = Eψ
2m µ ¶
−~2 ∂ 2 ψ ∂ 2 ψ ∂ 2 ψ
⇒ + 2 + 2 = Eψ. (26.10)
2m ∂x2 ∂y ∂z
It is generally true that when the Hamiltonian is a sum of independent terms, we
can write the wavefunction as a product of wavefunctions
where C is a constant.
184
So, f (x) is a constant. Similarly for g(y) and h(z)
Applying this to our Schrödinger equation means that we have converted our
partial differential equation into three independent ordinary differential equations,
−~2 1 d2 ψx −~2 d2 ψx
= Ex =⇒ = Ex ψx (26.16)
2m ψx dx2 2m dx2
−~2 1 d2 ψy −~2 d2 ψy
= Ey =⇒ = Ey ψy
2m ψy dy 2 2m dy 2
−~2 1 d2 ψz −~2 d2 ψz
= Ez =⇒ = Ez ψz
2m ψz dz 2 2m dz 2
which we recognize as the 1D particle in a box equations.
185
Degeneracy
The 3D particle in a box model brings up the concept of degeneracy.
When n(> 1) states have the same total energy they are said to be n-fold degen-
erate.
186
27. Operators
Definitions
— Rules
∗ Transitivity
∗ Associativity
∗ Existence of an identity
∗ Existence of an inverse
— e.g., Addition on the set of real numbers, Multiplication on the set of
real numbers
187
187
— Note: Commutivity is not a requirement of an algebra
∗ example 1: multiplication on the set of real number is commutive:
ab = ba
∗ example 2: multiplication on the set of n × n matrices is not com-
mutive: ab 6= ba in general. e.g.,
" #" # " #
1 0 3 1 3 1
= (27.1)
2 1 1 1 7 3
but " #" # " # " #
3 1 1 0 5 1 3 1
= 6= (27.2)
1 1 2 1 3 1 7 3
1. Equality:
if α̂ = β̂, then α̂f (x) = g(x) = β̂f (x) (27.3)
2. Addition:
3. Multiplication:
³ ´
α̂β̂f (x) = α̂ β̂f (x) (27.5)
β̂ α̂f (x) = β̂ (α̂f (x)) ,
4. Inverse:
188
Linear operators:
Hermitian operators:
Commutators:
We have seen that in general α̂β̂ 6= β̂ α̂. This leads to the construction of the
commutator, [◦, ◦]: h i
α̂, β̂ ≡ α̂β̂ − β̂ α̂. (27.7)
189
h i
If α̂β̂ = β̂ α̂, then α̂, β̂ = 0 and α̂ and β̂ are said to commute with one another.
If α̂f (x) = af (x) and β̂ and α̂ commute, then β̂f (x) = bf (x).
which states that β̂f is an eigenfunction of α̂ with eigenvalue a. The only way for
this to be true is if β̂f = bf.
190
27.2. Orthogonality, Completeness, and the Superposition
Principle
191
28. Angular Momentum
L=x×p (28.1)
Hence,
192
192
28.2. Quantum theory of Angular Momentum
So, in accordance with postulate II, we replace the classical variables with their
operators. That is,
µ ¶
~ ∂ ∂
L̂x = (ŷ p̂z − ẑ p̂y ) = y −z , (28.7)
i ∂z ∂y
µ ¶
~ ∂ ∂
L̂y = (ẑ p̂x − x̂p̂z ) = z −x , (28.8)
i ∂x ∂z
µ ¶
~ ∂ ∂
L̂z = (x̂p̂y − ŷ p̂x ) = x −y . (28.9)
i ∂y ∂x
Recall the basic commutators.
∙ ¸
∂
, u = 1, (28.10)
∂u
∙ ¸
∂
, v = 0,
∂u
where u, v = x, y, or z and u 6= v.
and h i h i h i
2 2 2
L̂ , L̂x = L̂ , L̂y = L̂ , L̂z = 0 (28.12)
193
∂
L̂z = −i~ (28.15)
∂φ
µ 2 ¶
2 2 ∂ ∂ 1 ∂2
L̂ = −~ + cot θ + (28.16)
∂θ2 ∂θ sin2 θ ∂φ2
The boundary condition for the particle in a box were ψ was zero outside the box.
Now the boundary condition is that ψ(φ) = ψ(φ + 2π). The wavefunction must
by 2π periodic.
194
m = 0, ±1, ±2, ±3, . . .
These wavefunctions are really the “same.” It will be most convenient to use
ψm (φ) = Aeimφ as our wave functions.
195
and
L̂− ≡ L̂x − iL̂y (28.26)
We collect here the commutators of L̂+ and L̂− :
h i
L̂z , L̂+ = L̂+ ⇒ L̂+ L̂z = L̂z L̂+ − L̂+ (28.27)
h i
L̂z , L̂− = −L̂− ⇒ L̂− L̂z = L̂z L̂− + L̂− (28.28)
Now, since L̂z and L̂2 commute there must exist a set of simultaneous eigenfunc-
tions {ψi }
L̂z ψi = mψ i (28.29)
and
L̂2 ψi = k2 ψi (28.30)
Physically, k~ represents the length of the angular momentum vector and m~
represents the projection onto the z-axis. (Note: for simplicity in writing we are
‘hiding’ the ~ in the wavefunctions.)
On these physical grounds we conclude |m| ≤ k, i.e., k sets an upper and lower
limit on m.
Now, at least one of the eigenfunctions in the set {ψ i } yields the eigenvalue mmax
(or l) when operated on by L̂z . Let’s call that eigenfunction ψl ;
L̂z ψl = lψ l . (28.31)
196
Using the commutator relation L̂− L̂z = L̂z L̂− + L̂− we get
³ ´
L̂z L̂− + L̂− ψl = lL̂− ψl (28.33)
L̂z L̂− ψl + L̂− ψl = lL̂− ψl
Bringing the second term on the left hand side over to the right hand side gives
L̂z L̂− ψl = lL̂− ψl − L̂− ψl (28.34)
L̂z L̂− ψl = (l − 1)L̂− ψl
| {z } | {z }
ψ l−1 ψ l−1
We see that L̂− ψl ≡ ψl−1 is in fact an eigenfunction of L̂z (with associated eigen-
value (l − 1)) and is thus a member of {ψi } .
The eigenfunction ψl−1 has an associated eigenvalue that is one unit less then the
maximum value.
The above procedure can be repeated n times so that L̂n− ψl = ψl−n provided n
does not exceed l − l0 .
The eigenfunction ψ l−n has an associated eigenvalue that is n units less then the
maximum value, i.e.,
L̂z ψl−n = (l − n)ψ l−n . (28.35)
The largest value of n is l − l0 . For that case,
L̂z ψl0 = (l − l + l0 )ψl0 = l0 ψl0 . (28.36)
Similar behavior is seen for the operator L̂+ , except in the opposite direction–the
eigenvalue is increased by one unit for each action of L̂+ . For example
L̂+ L̂z ψl0 = L̂+ l0 ψl0 (28.37)
³ ´
L̂z L̂+ − L̂+ ψl0 = l0 L̂+ ψl0
L̂z L̂+ ψl0 = (l0 + 1)L̂+ ψl0 .
197
The raising and lowering nature of L̂+ and L̂− is why they are called ladder
operators.
We can not act with L̂+ and L̂− indefinitely since we are limited by l–we reach
the ends of the ladder. This requires that
L̂+ ψl = 0 (28.39)
Often times the ladder operators appear in tandem either as L̂− L̂+ or L̂+ L̂− so it
is useful list some identities for these products
and
L̂+ L̂− = L̂2 − L̂2z + L̂z (28.41)
We can use these identities to derive a relation between the quantum numbers k
and l.
We begin with ³ ´
L̂− L̂+ ψl = L̂− L̂+ ψl = 0, (28.42)
Therefore
p
k2 − l2 − l = 0 ⇒ k = l(l + 1). (28.44)
198
We we can also consider
³ ´
L̂+ L̂− ψl0 = L̂+ L̂− ψl0 = 0 (28.45)
and ³ ´
L̂+ L̂− ψl0 = L̂2 − L̂2z + L̂z ψl0 = (k 2 − l02 + l0 )ψl0 . (28.46)
substituting in the relation we just found for k gives
simplifying gives
l = −l0 (28.48)
Thus mmax = l, mmin = −l and so m = l, l − 1, l − 2, . . . , −l + 1 , −l.
This also implies that the number of ‘rungs’ is 2l + 1 and that l must be either an
integer or a half-integer.
199
The spherical harmonics are functions of two variables, but they are a product of
a function only of θ and a function only of φ,
|m|
ψlm = Ylm (θ, φ) = APl (θ)eimφ , (28.52)
|m|
where the Pl (θ) are the Legendra polynomials and A is normalization constant.
Both the spherical harmonics and the Legendra polynomials are tabulated. They
are also built-in functions of Mathematica.
The spherical harmonics (and hence the angular momentum wavefunctions) are
orthonormal; meaning,
Z 2π Z π (
1 l0 = l and m0 = m
Yl∗0 m0 (θ, φ)Ylm (θ, φ) sin θdθdφ = (28.53)
0 0 0 l0 6= l or m0 6= m
Rotational energy
For general rotation in three dimensions the is
~2 2
Ĥ = L̂ , (28.54)
2I
so the Schrödinger equation is
~2 2 ~2
Ĥψ lm = Elm ψlm ⇒ L̂ ψlm = Elm ψlm ⇒ l(l + 1)ψlm = Elm ψlm . (28.55)
2I 2I
Thus
l(l + 1)~2 l(l + 1)h2
Elm = = = El . (28.56)
2I 8π2 I
There is no m dependence for the energy. In other words, the energy levels are
determined only by the value of l.
We know that there are 2l + 1 different m values for a particular l value. All 2l + 1
of these wavefunctions correspond to the same energy. We say the there is a 2l + 1
degeneracy of the energy levels.
200
29. Addition of Angular Momentum
One example of such a system is the spin of an electron, l = s = 1/2. The values
of m = ms are limited to +1/2 and −1/2.
One peculiarity of this system is that the wavefunctions are 4π periodic (and 2π
antiperiodic):
ψs (θ) = −ψs (θ + 2π) (29.1)
and
ψ s (θ) = ψs (θ + 4π). (29.2)
That means that the system has to ‘rotate’ twice (in spin space not coordinate
space) to get back to its original state.
201
201
29.2. Addition of Angular Momentum
In atoms the are a number of sources of angular momentum: The l’s and s’s of
each of the electrons.
The electrons in many electron atoms couple. The are two main coupling schemes
which account for the total angular momentum of the atom.
• works well for low atomic weight atoms (first couple of rows of the
periodic table)
P
• find the total spin angular momentum S = Ms,max , (Ms = i msi )
P
• find the total orbital angular momentum L = Mmax , (M = i mi )
• then J = L + S
2. jj coupling
Consider two sources of angular momentum for a system represented by the op-
erators Jˆ1 and Jˆ2 (Jˆ1 and Jˆ2 could be L̂ or Ŝ angular momentum; we use Jˆ when
we speak generally.)
202
The total angular momentum is JˆT = Jˆ1 + Jˆ2 .
The last statement implies that the orientation quantum number of the total
system is simple the sum of that for the components
M = m1 + m2 (29.3)
We need to determine the allowed values of the total angular momentum quantum
number J.
The minimum value of J is determined by the case when the components add in
the least favorable manner. That is,
The total angular momentum is quantized is exactly the same manner as any
other angular momentum. Thus the allowed values of J are
The table below shows the total spin angular momentum S for a two electron
system
203
spin state ms1 ms1 MS S
1 1
α(1)α(2) 2 2
1 1
β(1)β(2) − 12 − 12 −1 1
α(1)β(2) + β(1)α(2) 0 0 0 1
α(1)β(2) − β(1)α(2) 0 0 0 0
Counting states:
The spin degeneracy, gS , of the states is given by 2S + 1. In the above example
the degeneracy is gS = 3 for the S = 1 states and gS = 1 for the S = 0 states.
We have already seen several term symbols, those being 1 S and 3 S during our
discussion of helium.
Term symbols are simply shorthand notion used to identify states. Term symbols
are useful for predict and understanding spectroscopic data. So, it is worthwhile
to briefly discuss them.
In general the term symbol is simply notates the total orbital angular momentum
and spin degeneracies of a particular set of states (or a state in the case of a singlet
state).
For historical reasons L values are associated with a letter like the l values of a
hydrogenic system are.
L 0 1 2 3 4 5
.
symbol S P D F G H
204
The term symbol for a particular states is constructed from the following general
template
gS
LJ .
Many electron atoms have term symbols associated with their states.
Rules:
1. All closed shells have zero spin and orbital angular momentums: L = 0,
S = 0. These states are all singlet S states, notated by 1 S
A charge possessing angular momentum has a magnetic dipole associated with it.
205
where A is the spin—orbit coupling constant.
From the Hamiltonian the spin—orbit interaction energy is
hcA
ESO = [J(J + 1) − L(L + 1) − S(S + 1)] (29.8)
2
206
30. Approximation Techniques
As we learned last semester, there are very few models for which we can obtain
an exact solution.
Last semester, we always took the simplest approximation to give the qualitative
properties of the unsolvable system.
• Treat the difference between the two systems as a perturbation to the solv-
able system
• These wavefunctions are used to find a first order correction to the energy.
207
207
• The first order energy is then used to make a first order approximation to
the wavefunction.
This process get algebraically intensive so we will only go as far as listing the first
order energy correction.
• Consider the quartic oscillator described by the potential V (x) = 12 kx2 +ax4
where a is very small and can be treated as a perturbation.
208
• For example, the ground state energy correction is then calculation from
Z ∞
(1) (0)∗ (0)
E0 = ψ0 Ĥ (1) ψ0 dx (30.5)
−∞
Z ∞
2 2
= A0 e−αx /2 ax4 A0 e−αx /2 dx
−∞
Z ∞
2 2
= aA0 x4 e−αx dx
√ −∞
3 πaA20
= 5 ,
4α 2
so the first order ground state energy for a quartic oscillator is
√
~ω 3 πaA20
E0 ' + 5 .
2 4α 2
The basic idea behind the variational method is to use a trial wavefunction with
an adjustable parameter. The value of the parameter which minimizes the energy,
Etrial , gives a trial wavefunction which is closest to the real wavefunction.
Etrial ≥ E.
The trial energy is now a function of the adjustable parameter, p, that we use to
minimize the trial energy by setting
dEtrial
=0 (30.7)
dp
209
and solving for p. (Strictly speaking we should check that we have a minimum
and not a maximum or inflection point, but with reasonably good trial functions
one is pretty safe in having a minimum.)
210
31. The Two Level System and
Quantum Dynamics
Our entire discussion of quantum mechanics thus far had dealt only with time
independent quantum mechanics.
Obviously there are cases where quantum objects move with time. For example,
firing an electron down a particle accelerator.
We shall finally get to quantum dynamics in this chapter, but first we will discuss
the very important model of the two level system.
If the harmonic oscillator is the most important model in all a physics, the two
level system is a close second.
The two level system is inherently quantum mechanical in nature. Unlike the
harmonic oscillator it has no classical analogue.
211
211
Consequently, we can not use our usual procedure of writing down the classical
Hamiltonian and then replacing the variables with their corresponding operators.
The two level system consists of two states ψ1 and ψ2 separated by energy 4 =
2 − 1 as shown below
where δ j,° “projects out” the j th state of the wavefunction being acted on.
212
For example let some arbitrary wavefunction ψ = aψ 1 + bψ2 , then
We can invert above equations and solve for ψ1 and ψ2 in terms of ψL and ψR
1 1
ψ1 = √ ψL + √ ψR (31.6)
2 2
and
1 1
ψ2 = √ ψL − √ ψR . (31.7)
2 2
213
31.2. Quantum Dynamics
So far we have been concerned with the eigenfunctions and eigenvalues (energy
levels) of the various quantum systems that we have discussed.
What has been kept hidden up to now is the fact that the eigenfunctions are really
multiplied by a phase factor of the form .
i
Ψn (x, t) ≡ ψn (x)e− ~ En t (31.8)
We can verify this by obtaining the time independent Schrödinger equation from
the more general time dependent
∂Ψn (x, t)
i~ = ĤΨn (x, t) (31.9)
∂t
i
∂ψn (x)e− ~ En t i
i~ = Ĥψn (x)e− ~ En t
∂t
i
∂e− ~ En t i
i~ψ n (x) = Ĥψn (x)e− ~ En t
µ ¶ ∂t
i i i
i~ψ n (x) − En e− ~ En t = Ĥψn (x)e− ~ En t
~
i i
En ψn (x)e− ~ En t = e− ~ En t Ĥψn (x)
En ψn (x) = Ĥψ n (x) (31.10)
Does this mean the eigenstates are not stationary states? To determine this we
need to calculate the probability of finding the particle in the same eigenstate at
some future time. This is given by
¯Z ¯2
¯ ¯
P (x, t) = ¯¯ Ψn (x, 0)Ψn (x, t)dx¯¯
∗
(31.11)
¯Z ¯2
¯ i ¯
= ¯¯ ψ n (x)ψ n (x)e ~ dx¯¯
∗ − En t
¯ Z ¯2
¯ −iE t ¯
¯
= ¯e ~ n
ψn (x)ψ n (x)dx¯¯
∗
¯ i ¯
¯ − ~ En t ¯2
= ¯e (1)¯ = 1,
214
so no matter what time t we check we will always find the system in the same
eigenstate. Thus the eigenstates are stationary states.
In general the state of the system need not be in one particular eigenstate; it may
be in a superposition of any number of eigenstates.
The “left” and “right” wavefunctions that we saw in the discussion of the two
level system are examples of superposition states.
¯Z µ ¶µ ¶¯2
¯ 1 ∗ 1 ∗ 1 − ~i E1 t 1 ¯
− ~i E2 t ¯
= ¯ ¯ √ ψ1 (x) + √ ψ2 (x) √ ψ1 (x)e + √ ψ2 (x)e
2 2 2 2 ¯
¯ Z Ã ! ¯
¯1 i i
ψ ∗1 (x)ψ 1 (x)e− ~ E1 t + ψ∗1 (x)ψ 2 (x)e− ~ E2 t ¯2
¯ ¯
= ¯ − ~i E1 t − ~i E2 t
dx¯ . (31.14)
¯2 ∗
+ψ2 (x)ψ 1 (x)e ∗
+ ψ2 (x)ψ 2 (x)e ¯
The “cross-terms” (those of the form ψ∗1 (x)ψ 2 (x) and ψ ∗2 (x)ψ 1 (x)) are zero when
215
integrated because the eigenfunctions are orthogonal. This leaves
¯Z ¯2
¯ ¯
P (x, t) = ¯ Φ (x, 0)Φ(x, t)¯¯
¯ ∗
(31.15)
¯ Z ³
¯1 i i
´ ¯¯2
= ¯¯ ψ 1 (x)ψ 1 (x)e ~ 1 + ψ2 (x)ψ 2 (x)e ~ 2 dx¯¯
∗ − E t ∗ − E t
2
¯ µ Z Z ¶¯2
¯1 − i E t i ¯
= ¯¯ e ~ 1 ∗
ψ1 (x)ψ 1 (x)dx + e ~ − E 2 t
ψ2 (x)ψ 2 (x)dx ¯¯
∗
2
¯ ³ ´¯¯2 1 ³ i ´³ i ´
¯1 − i E t − ~i E2 t ¯ + ~i E2 t − ~i E2 t
¯
= ¯ e ~ 1
+e = e+ ~ E1 t
+ e e− ~ E1 t
+ e
2 ¯ 4
1 ³ ´ 1µ (E1 − E2 )
¶
+ ~i (E1 −E2 )t − ~i (E1 −E2 )t
= 1+e +e +1 = 1 + cos t .
4 2 ~
The probability of find in the system in its original superposition states is not one
for all times t.
216
Key Equations for Exam 1
Listed here are some of the key equations for Exam 1. This section should not
substitute for your studying of the rest of this material.
The equations listed here are out of context and it would help you very little to
memorize this section without understanding the context of these equations.
The equations are collected here simply for handy reference for you while working
the problem sets.
Equations
217
217
• The Laplacian µ ¶
2 ∂2 ∂2 ∂2
∇ = + + . (31.19)
∂x2 ∂y 2 ∂z 2
• Normalized wavefunctions for the 3D particle in a box,
√
2 2 nx πx ny πy nz πz
ψn (x) = √ sin sin sin . (31.20)
abc a b c
• Orthonormality: (
Z
1, j=k
ψ∗j ψk = . (31.22)
space 0, j 6= k
• Superpostion:
X
ψ= ai ϕi (31.23)
i
and h i h i h i
2 2 2
L̂ , L̂x = L̂ , L̂y = L̂ , L̂z = 0. (31.25)
~2 m2 m2 h2
Em = = . (31.26)
2I 8π2 I
218
• The eigenfunctions of angular momentum are entirely specified by two quan-
tum numbers l and m: ψ lm .
l(l + 1)~2
El = . (31.29)
2I
gJ = 2J + 1. (31.30)
• In general
i
Ψn (x, t) ≡ ψn (x)e− ~ En t (31.33)
219
Part VI
220
220
32. Symmetry and Group Theory
We now take a short break from physical chemistry to discuss ideas from the
mathematical field of group theory.
• The mathematical properties of all the possible groups have been worked
out
— Bonding
— Properties of wavefunctions
— Vibrational modes
— Many more applications
221
221
32.1. Symmetry Operators
Any operator that leaves |ψ|2 invariant are symmetry operators for that particular
system:
Ô |ψ|2 = |ψ|2 . (32.1)
This implies
Ôψ = ±ψ. (32.2)
That is, the eigenvalues for the particular symmetry operator are 1 or −1.
For molecules we will be dealing with point group symmetry operators. These
operators deal with symmetry about the center of mass.
In mathematics the term “group” has special meaning. It is a set of objects and
a single operation, which has the following properties.
222
3. The “product” of any two members of the group yield a member of the
group.
4. The inverse of every member of the group is also in the group. In other
words, for any member of the group one can find another member of the
group which, upon “multiplication,” yields the identity element.
The C2v group consists of the symmetry elements Ê, Ĉ2 , σ̂ v (in-plane) and σ̂ 0v
(transverse).
C2v Ê Ĉ2 σ̂ v σ̂ 0v
Ê Ê Ĉ2 σ̂ v σ̂ 0v
Ĉ2 Ĉ2 Ê σ̂ 0v σ̂ v
σ̂ v σ̂ v σ̂ 0v Ê Ĉ2
σ̂ 0v σ̂ 0v σ̂ v Ĉ2 Ê
223
Connecting with the C2v group example lets consider the wavefunctions for water.
In this case one can collect the eigenvalues (either +1 or −1) for each of the four
symmetry operators as a four component vector. As it turns out there is four
possible sets of eigenvalues–hence four different vectors:
A1 = (1, 1, 1, 1)
A2 = (1, 1, −1, −1)
B1 = (1, −1, 1, −1)
B2 = (1, −1, −1, 1).
To see where these four vectors come from, consider the following.
• Finally there is a restriction do to the fact that the eigenvalues must obey
the group multiplication table.
— This restriction forces the eigenvalues of σ̂v and σ̂ 0v to be the same for
the A type vectors and opposite for the B type vectors.
224
The above considerations leave four vectors.
In fact, there will always be the same number of vectors as symmetry elements.
C2v Ê Ĉ2 σ̂ v σ̂ 0v
A1 1 1 1 1
A2 1 1 −1 −1
B1 1 −1 1 −1
B2 1 −1 −1 1
We shall investigate how degeneracies of energy levels are broken as one reduces
the overall symmetry of the system.
225
In doing this we will, for simplicity, consider only proper rotations (Cn ). Mirror
symmetry will not be considered (although in real applications one must consider
all symmetry).
First consider a free atom. In this case there is complete rotational symmetry.
Thus the symmetry group is the spherical group (see character table handout.)
This is the group associated with the particle on a sphere model and the angular
part of the hydrogen atom. The vectors are the labeled according to the angular
momentum quantum numbers S, P, D, F, etc.
Now consider the free atom being placed in a crystal lattice of octahedral sym-
metry. For example placed at the center of a cube which has other atoms at the
centers of each face of the cube.
When moving to octahedral symmetry we now must look at the character table for
such a case–the O group (remember we are considering only proper rotations).
The S vector has the symmetry of a sphere (x2 + y 2 + z 2 ) and hence is totally
symmetric. It is also nondegenerate so it will be, of course, nondegenerate in
the octahedral case. It remains totally symmetric so it is now represented by the
vector A1 .
The P vector is triply degenerate and has the symmetry of x, y and z as we see
from the character table for the spherical group. In the octahedral crystal the
degeneracy remains in tact and these states are represented by the T1 group.
226
The D vector has a degeneracy of five and the symmetry of 2z 2 − x2 − y 2 , xz, yz,
xy, x2 − y 2 . Looking at the table for the O group we see the degeneracy splits:
two states become E type and the remaining three become T2 type.
The octahedral group is still highly symmetric. Lets say that two atoms on oppo-
site sides of the cube are moved slightly inward. The remaining four atoms remain
in place.
This breaks the octahedral symmetry and the system now assumes D4 symmetry.
Now the A1 vector of the O group becomes the A1 vector of the D4 group. The
triply degenerate T1 vector splits into a A2 state and a doubly degenerate E state.
The E states from the O group become a A1 type state and a B1 type state.
The T1 states from the O group become a A2 type state and a E type state.
227
33. Molecules and Symmetry
From our chapter on diatomic molecules last semester we have learned a great
deal which caries over directly to polyatomic molecules.
So, in this chapter we simply investigate some of the specific details regarding
polyatomic molecules.
This now leaves one with 3N − 5 vibrational degrees of freedom for linear poly-
atomic molecules and 3N − 6 vibrational degrees of freedom for nonlinear mole-
cules.
228
228
33.1.1. Normal Modes
The number of normal modes equals the number of vibrational degrees of freedom.
At low energies the normal modes are well approximated as harmonic oscillators.
The symmetry of the normal modes are associated with entries in the character
table of the point group of any particular polyatomic molecule.
Example: Water
The point group symmetry of the water molecule is C2v . The character table is
C2v Ê Ĉ2 σ̂ v σ̂ 0v
A1 1 1 1 1
A2 1 1 −1 −1
B1 1 −1 1 −1
B2 1 −1 −1 1
Water has three nuclei and it is nonlinear so it has 3(3) − 6 = 3 normal modes.
The three modes are the bending vibration, the symmetric stretching vibration
and the asymmetric stretch.
229
The normal modes are associated with a particular vector (row) of the character
table by considering the action of the each of the symmetry elements on the normal
mode.
For the bending mode, the vibration is complete unchanged by any of the sym-
metry elements. Consequently the bending mode is associated with A1
The same is true for the symmetric stretching mode. It too is associated with A1 .
The asymmetric stretch, however, is associated with B1 since Ĉ2 and σ̂0v transform
the mode into its opposite and σ̂ v leaves it unchanged.
230
34. Vibrational Spectroscopy and
Group Theory
We now investigate how group theory and, in particular, the character tables can
be used to determine IR and Raman spectra and selection rules for polyatomic
molecules
34.1. IR Spectroscopy
The typical “energies” for IR absorption are from 400 to 4000 cm−1 . This is in
the Infrared region of the electromagnetic spectrum.
As for electronic absorption one typically employs the electric dipole approxima-
tion.
• Multipole expansion
231
231
• Light—matter interaction is dominated by the light—dipole coupling so the
other interactions are ignored.
The upshot of all this is as far as group theory is concerned is the following
selection rule:
• The vibrational coordinates for an IR active transition must have the same
symmetry as either x, y, or z for the particular group.
Example: Water
Recall that the point group symmetry of the water molecule is C2v .
We now need a column of the character table which we have ignored up to this
point.
The last column describes the symmetry of several important functions for the
point group.
232
Among these functions are x, y, and z.
So we can see immediately that the IR active modes of any molecule having this
point group will be A1 , B1 , and B2 .
The A2 mode is IR forbidden and any vibrations having this symmetry will not
appear in the IR spectrum (or it may appear as a very weak line).
From before we know the modes of water have A1, and B1 symmetry and hence
are all IR active and appear in the IR spectrum
The light loses energy to the material in an amount equal to the vibrational energy
of the molecules is the sample.
This lose of energy shows up in the scattered light as a new down shifted frequency
from that of the original input light frequency.
233
↔
The molecular quantity of interest is the polarizability tensor, α.
We will not get into tensors in this course except to say the polarizability tensor
elements are proportional to the quadratic functions, x2 , y 2 , z 2 , xy, xz, yz, (or
any combinations thereof).
One can now inspect the character table to determine which modes will be Raman
active.
234
35. Molecular Rotations
Recall that the three degrees of freedom that described the position of the nuclei
about the center of mass were (R, θ, φ). The R was involved in vibrations. We
now turn our attention to the angular components to describe rotations.
Recall also the Kinetic energy operator for the nuclei in the center of mass coor-
dinates
~2 ˆ 2 ~2 ∂ 2 ∂ ~2 ˆ2
T̂N = − ∇N = − R̂ + J . (35.1)
2μ 2μR2 ∂R ∂R 2μ
We will now be concerned only with the angular part,
~2 ˆ2
−
J . (35.2)
2I
Now, under the Born-Oppenheimer approximation, R is a parameter. For constant
R the rotational energy is given by
J(J + 1)~2 J(J + 1)h2
Erot = = . (35.3)
2μR2 8π 2 I
This is the so-called rigid rotor energy.
It is common to define
h
Be ≡ (35.4)
8π 2 I
as the rotational constant. Then
with a degeneracy of
gJ = 2J + 1 (35.6)
235
235
35.1. Relaxing the rigid rotor
Of course the rigid rotor is not a perfectly correct model for a diatomic molecule.
There are two corrections we will now make
2. Centrifugal stretching:
−J 2 (J + 1)2 Dc , (35.8)
where
4Be3
Dc ≡ (35.9)
ω̃ 2e
is the centrifugal stretching constant.
A rotational transition can occur in the same vibrational level n. This is called a
pure rotational transition. Alternatively, a rotational transition can accompany a
vibrational transition.
236
It turns out that typical rotational energy gaps are on the order of a few wavenum-
bers or less.
Thermal energy, kT, at room temperature is about 200 cm−1 . This means that
at room temperature the many excited rotational states are populated.
∗ ∗ ∗ See Handout ∗ ∗∗
The selection rules and the thermalized states combine to yield a multi-peaked
ro-vibrational spectrum.
∗ ∗ ∗ See Handout ∗ ∗∗
There are a few additional details regarding rotations for polyatomic molecules as
compared to diatomics
Of course one could set-up an arbitrary center of mass coordinate system. But
one system is special–the principle axes coordinate system.
The principle axes coordinate system is the one in which the z-axis is taken to be
along the principle symmetry axis.
237
There are four classes of polyatomic molecules regarding rotations
where
h
B= (35.13)
8π2 Ixx
2. Symmetric tops (e.g., benzene)
• Ixx = Iyy
• Jˆ2 = Jˆx2 + Jˆy2 + Jˆz2
• The Hamiltonian is
" #
~2 Jˆx2 + Jˆy2 Jˆz2
Ĥ = + (35.14)
2 Ixx Izz
where
h
A= , (35.16)
8π 2 Izz
h
B= 2 (35.17)
8π Ixx
and K is the quantum number describing the projection of the angular
momentum onto the z-axis
238
3. Spherical tops (e.g., methane)
where
h
B= (35.20)
8π2 Ixx
4. Asymmetric tops
239
36. Electronic Spectroscopy of
Molecules
The electronic spectra of molecules are quite different than that of atoms.
Atomic spectra consist of single sharp lines due to transitions between energy
levels.
Molecular spectra, on the other hand, have numerous lines (bands) due to the
fact that electronic transitions are accompanied by vibrational and rotational
transitions.
240
240
In the figure below the ground and first excited electronic levels (as a function of
R) are shown.
Note: The potential minima are not at the same value of R for each of the
electronic states.
241
∗ ∗ ∗ See Spectroscopy Supplement p2 ∗ ∗∗
• Light promotes the system from the ground vibrational and ground elec-
tronic state to excited vibrational levels in the excited electronic state.
• The system then very rapidly (on the order of tens to hundreds of fem-
toseconds) relaxes to the ground vibrational state of the excited electronic
state.
• The molecule than emits a photon to drop back down into an excited vibra-
tional state of the ground electronic state.
• This requires a lower energy (or “more red”) photon. Hence the Stokes shift.
242
36.2. Franck—Condon activity
We have seen than an electronic tranistion involves not only a change in the
electronic state but also in the vibrational state in general (and in the rotaitonal
state as well, but we will ingore this).
Assuming the electronic transition is allowed one must calculate the probability of
the vibrational transistion as well. This is down by evaulating the Franck—Condon
integral.
The Franck—Condon principle states that the nuclei do not move during an elec-
tronic transition.
Mathematically this means that the strength of a transition from Ψi = ψel,i ψvib,i →
Ψf = ψel,f ψvib,f is given by
¯Z ¯2 ¯Z Z ¯2
¯ ¯ ¯ ¯
¯ ¯ ¯ ¯
¯ Ψ∗f μ̂el Ψi ¯ = ¯ ψ∗el,f ψ∗vib,f μ̂el ψel,i ψvib,i ¯ , (36.1)
¯ all ¯ ¯ el vib ¯
space space space
243
where μ̂el is the electronic transition dipole. We can separate the integrals as
¯Z ¯2 ¯Z ¯2
¯ ¯¯ ¯
¯ ∗ ¯ ¯ ∗ ¯
¯ ψel,f μ̂el ψel,i ¯ ¯ ψvib,f ψvib,i ¯ , (36.2)
¯ el ¯ ¯ vib ¯
space space
| {z }| {z }
if 6=0, allowed Franck—Condon
244
37. Fourier Transforms
Furthermore, if the signal decays rapidly it will have a broad spectrum and, con-
versely, if the signal decays slowly it will have a narrow spectrum. The mathemat-
ics which governs these qualitative statements is Fourier transform theory which
we now review.
245
245
The Fourier transformation is unique and it has a unique inverse, =−1 , which is
given by Z ∞
h i 1
−1 ˜ ˜ −iωt
= f (ω) = f (t) = f(ω)e dω. (37.2)
2π −∞
The above two relations form the convention used throughout this work.
Other authors use different conventions, so one must take care to know exactly
which convention is being used.
For simplicity the symbol = will be used to represent the Fourier transformation
operation, i.e., = [f (t)] = f˜(ω). Whereas
h
−1
i the symbol = will represent the inverse
Fourier transformation, i.e., =−1 f(ω) ˜ = f(t).
246
Key Equations for Exam 2
Listed here are some of the key equations for Exam 2. This section should not
substitute for your studying of the rest of this material.
The equations listed here are out of context and it would help you very little to
memorize this section without understanding the context of these equations.
The equations are collected here simply for handy reference for you while working
the problem sets.
Equations
— linear: 3N − 5
— not linear: 3N − 6
where
h
Be ≡ (37.4)
8π 2 I
is the rotational constant.
247
247
• The degeneracy of the rigid rotor is
gJ = 2J + 1 (37.5)
• Franck—Condon Factor: ¯Z ¯2
¯ ¯
¯ ¯
¯ ψ∗vib,f ψvib,i ¯ (37.6)
¯ vib ¯
space
248
Part VII
249
249
38. Physical Kinetics
We now turn our attention to the molecular level and in particular to molecular
motion.
Consider a gas of point mass (m), m is the molecular (or atomic) mass
250
250
The number of particles, NVv , having velocities in a macroscopic volume, Vv , in
velocity space is
Z Z Z Z
NVv = N F (v, t)dv = N F (vx , vy , vz , t)dvx dvy dvz (38.1)
Vv Vv
If we choose the origin of our coordinate system to be at the center of mass of the
gas, then for many cases the velocity distribution will be isotropic–independent
of θ and φ.
F (v, θ, φ, t) = F (v, t). (38.2)
251
We shall consider stationary isotropic distributions F (v). So F (v) represents a
distribution of speeds.
It can be shown from first principles that
µ ¶ 32
m −mv 2
F (v) = 4π e 2kb T v 2 (38.4)
2πkb T
252
• Particles are hard spheres of radius σ.
• The number of collisions equals the number of particles with their centers
in V :
number of collisions = n∗ πσ 2 v4t (38.6)
For the above model we need to find the average collision frequency. Since the
molecules are moving relative to one another we must find the average relative
velocity, v̄12 = h|v1 − v2 |i
From the above expression one defines the mean free path λ to be
/v̄ LP
n∗ = RT RT
λ= √ = √ (38.8)
2n∗ πσ 2/v̄ 2P Lπσ 2
253
39. The Rate Laws of Chemical
Kinetics
We can, from thermodynamics, address the question; Will the reaction occur?
We need kinetics, however, answer the question: How fast will the reaction occur?
aA + bB = cC + dD (39.1)
The time dependence of this reaction can be observed by following the disap-
pearance of either of the reactants or appearance of either of the products. That
is,
d[A] d[B] d[C] d[D]
− or − or or (39.2)
dt dt dt dt
BUT this is ambiguous because a moles of A reacts with b moles of B and a does
not, in general, equal b. We must account for the stoichiometry.
254
254
We define the reaction velocity as
1 d[I]
v= (39.3)
vi dt
where vi = −a, −b, c or d and I = A, B, C, or D.
This definition is useful but must be used with caution since for complicated
reactions all the v’s may not be equal. An example of this is
½
bB → cC + dD
aA + (39.4)
b B0 → c0 C0 + d0 D0
0
A rate law is the mathematical statement of how the reaction velocity depends
on concentration.
v = f (conc.) (39.5)
Many, but certainly not all, rate laws are of the form
Note that we shall use an equal sign when talking about the overall reaction and
arrows when talking about the elementary reactions
Example
255
Let
2A + 2B = C + D (39.8)
The rate laws for elementary reactions can be determined from the stoichiometry
Conversely, rate laws for overall reactions can not be determined by stoichiometry.
Connection to thermodynamics
Consider the overall or elementary reaction
kf
aA + bB cC + dD (39.9)
kr
where kf is the rate constant for the reaction to proceed in the forward direction
and kr is the rate constant for the reaction to proceed in the reverse direction.
256
bringing kr to the LHS and [A][B] to the RHS we get
kf [C]c [D]d
= a b
= Kc0 (39.11)
kr [A] [B]
where Kc0 is the thermodynamic equilibrium “constant.”
H2 + I2 = 2HI. (39.12)
The observed rate laws are vf = kf [H2 ][I2 ] and vr = kr [HI]2 . This suggests that the
reaction is elementary. In fact, the reaction is not elementary. Moral: Kinetics
is very much an empirical science.
Next consider the reaction between molecular hydrogen and molecular bromine,
The above two example are seemingly very similar but they have very different
observed rate laws. Moral: Kinetics is very much an empirical science.
257
• To establish empirical rate laws
Concentrations c(t) are measured not rates. To obtain the rate from the concen-
tration we must take its time derivative dc(t)
dt
. That is we must measure c(t) as a
function of time and find the rate of change of this concentration curve.
The rates of chemical reactions vary enormously from sub-seconds to years. Con-
sequently no one experimental technique can be used.
• For slow reactions (hrs/days) almost any technique for measuring the con-
centration can be used.
• Very fast (sec/subsec) reactions cause problems because the reaction goes
faster than one can mix the reactants.
258
39.2.1. Differential methods based on the rate law
Methods based directly on the rate law rely on the determination of the time
derivative of the concentration.
The main problem with such a method is that randomness in the concentration
measurements gets amplified when taking the derivative.
2. Method of isolation
The above differential methods look directly at the rate law which is a differential
equation. The differential equation is not solved.
259
We now solve the differential equations to yield what are called the integrated
rate law.
The differential equations (rate law) and their solutions (integrated rate law) are
simply listed here for a few rate laws.
type rate lawa) integrated rate lawa)
1 d[I]
1st order vi dt
= k[I] [I] = [I0 ]evi kt
1 d[I] 1
2nd order vi dt
= k[I]2 [I]
= [I10 ] − vi kt
1 d[I] 1 1
nth orderb) vi dt
= k[I]n [I]n−1
= [I0 ]n−1
− (n − 1)vi kt
d[I]
enyzme 1
vi dt
= kmk[I]
+[I]
km ln [I[I]0 ] + ([I0 ] − [I]) = −vi kt
a)
[I] is the concentration of one of the reactants in an elementary reaction and
vi is the stoichiometric factor for [I] (n.b., vi is a negative number).
b)
The order need not be an integer. For example n = 3/2 is a three-halves
order rate law.
260
40. Temperature and Chemical
Kinetics
261
261
Substituting the Arrhenious equation for the rate constants gives
∙ Ea
¸ h i
Ear
− RTf
ln Ka = ln Af e − ln Ar e− RT (40.6)
∙ ¸
Af Ear − Eaf
= ln +
Ar RT
Ea = E 0 + jRT (40.8)
and
A = aT j ej (40.9)
We can verify this by starting with the Arrhenious equation and substituting the
above expressions,
Ea E 0 +jRT −E 0 −E 0 √
k = Ae− RT = aT j ej e− RT = aT j e/j e/
−j
e RT = aT j e RT (40.10)
262
— Collision frequency for A–B collisions
s
8RT
zAB = πσ AB L2 [A][B] (40.11)
πLμ
mA mB
where μ ≡ mA +mB
is the reduced mass and σAB is the collision diameter.
zA B
• The maximum reaction velocity is vmax = L
, but intuitively the actual
reaction velocity will be less because
263
• Comparison to the (temperature corrected) Arrhenious equation suggests
s
8RT 1
A = pπσ AB L e2 (40.15)
πLμ
and
1
Ea = Emin + RT (40.16)
2
• The active complex is a state in the thermodynamic sense, thus we can apply
thermodynamics to it.
a‡ low [‡]
Ka‡ = ' (40.18)
aA aB conc. [A][B]
264
• Definition: transmission factor, f
• The reaction rate constant for reactants going to products for ACT is
kb T ‡
k = f Ka‡ = K (40.19)
h a
• Thermodynamics tells us that
where 4G‡ = 4H ‡ − T 4S ‡ .
Up to now, the reactions we have studied have been single step reactions.
265
• Parallel reactions are of the form, for example,
k
A + B1 →1 C (40.23)
k2
A + B2 → D
• The rate constant for the disappearance of [A] is simply the sum of the two
rate constants: k = k1 + k2
Series reactions:
d[A]
− = k1 [A]
dt
d[B]
= k1 [A] − k2 [B]
dt
d[C]
= k2 [B],
dt
which, when solved yields
266
40.4. Chain Reactions
Chain reactions are reactions which have at least one step that is repeated indef-
initely. The simplest chain reactions have three distinct steps (discussed below)
267
2. Propagation: The radical formed in the initiation step reacts with some so
molecule M0 to form another molecule M00 and another radical R0 ·. This step
repeats an indefinite number of times.
R·+M0 → M00 + R0 ·.
3. Termination: The radicals interact with each other or with the walls of the
container to forma stable molecule
R0 ·+R0 · → M000
or
R0 ·+wall → removed
268
41. Gases and the Virial Series
Unlike liquids and solids, a particular particle has much less significant interactions
with the other particles.
Recall from last semester several of the equations of states for gases.
P V = nRT. (41.1)
m
The equation of state can also be expressed in term of density ρ = V
mP
ρ= . (41.2)
nRT
• The van der Waals gas equation of state
nRT n2 a
P = − 2 (41.3)
V − nb V
or
RT a
P = − 2, (41.4)
Vm − b Vm
where the parameter a accounts for the attractive forces among the particles
and parameter b accounts for the repulsive forces among the particles
269
269
• Berthelot
nRT n2 a RT a
P = − 2
= − (41.5)
V − nb T V Vm − b T Vm2
• Dieterici an a
nRT e− RT V RT e− RT Vm
P = = (41.6)
V − nb Vm − b
• Redlich-Kwang
nRT n2 a RT a
P = −√ = −√ (41.7)
V − nb T V (V − nb) Vm − b T Vm (Vm − b)
n
The virial series in powers of V
is
³n´ ³ n ´2 ³ n ´3
z = 1 + B(T ) + C(T ) + D(T ) +··· , (41.8)
V V V
or µ ¶ µ ¶2 µ ¶3
1 1 1
z = 1 + B(T ) + C(T ) + D(T ) + ··· . (41.9)
Vm Vm Vm
B(T ), C(T ), etc. are called the virial coefficients.
270
41.2.1. Relation to the van der Waals Equation of State
P Vm Vm R //T / a
V
= − m /2
RT //
R T Vm − b RT Vm
Vm a
= −
Vm − b RT Vm
1 a
= b
− (41.11)
1 − Vm RT Vm
P Vm
but RT
= z so
1 a
z= b
− . (41.12)
1 − Vm RT Vm
1
The first term is of the form 1−x
which has the power series expansion
1
= 1 + x + x2 + · · · . (41.13)
1−x
Therefore µ ¶2
a b b
z=− +1+ + + ··· . (41.14)
RT Vm Vm Vm
1 1
the first term is proportional to Vm
and so it can be combined with the Vm
term
in the series expansion, hence
³ µ ¶2
a ´ 1 b
z =1+ b− + + ··· . (41.15)
RT Vm Vm
This series can now be compared term by term to the virial series to give expression
for the virial coefficients:
³ a ´
B(T ) = b − , C(t) = b2 , D(T ) = b3 , etc. (41.16)
RT
271
41.2.2. The Boyle Temperature
z = 1 + B 0 (T )P + C 0 (T )P 2 + D0 (T )P 3 + · · · . (41.18)
The relation of this expansion to the one in V1m can be obtained. One finds (see
homework)
B(T )
B 0 (T ) = , (41.19)
RT
272
C(T ) − B(T )2
C 0 (T ) = (41.20)
(RT )2
and
D(T ) − 3B(T )C(T ) − 2B(T )3
D0 (T ) = (41.21)
(RT )3
The virial coefficients can be estimated using empirical equations and tabulated
parameters.
• Estimates based on critical values (we will discuss critical values shortly, for
now treat them as empirical parameters):
µ ¶
9RTc 6Tc2
B(T ) = 1− 2 . (41.25)
128Pc T
273
42. Behavior of Gases
We shall briefly consider the P, V and T behavior of dense fluids (e.g., liquids).
• Positive α means the volume of the fluid increases with increasing temper-
ature.
• Positive κT means the volume of the fluid decreases with increasing pressure.
274
274
42.1.1. α and κT for an ideal gas
As an exercise we shall calculate α and κT using the ideal gas equation of state
(n.b., it is, of course, absurd to treat a liquid as an ideal gas). Starting with the
ideal gas law: V = nRT P
.
µ ¶ Ã ¡ ¢! µ ¶
−1 ∂V −1 ∂ nRT P −1 nRT
κT = = = − 2 (42.2)
V ∂P T V ∂P V P
T
1 nRT 1 / //
nR T 1
= = =
(P V ) P
| {z }
/n R
//T P P
=nRT
and µ ¶ Ã ¡ ¢!
1 ∂V 1 ∂ nRT
P 1 1
α= = = /n R
/ = (42.3)
V ∂T P V ∂T VP
|{z} T
P
/R
=n /T
In general, the compressibility and expansion of liquids (and solids) are very small.
So one can expand the volume in a Taylor series about a known pressure, P0 .
At constant T
µ ¶ µ ¶2
∂V ∂V
V (P ) = V0 + (P − P0 ) + (P − P0 )2 + · · · (42.4)
∂P ∂P T
| {z T}
−V0 κT
so,
V (P ) ≈ V0 [1 − κT (P − P0 )] . (42.5)
This approximation is quite good even over a rather large pressure range (P −P0 =
100 atm or so).
275
Likewise at constant P
¶
µ µ ¶2
∂V ∂V
V (T ) = V0 + (T − T0 ) + (T − T0 )2 + · · · (42.6)
∂T P ∂T T
| {z }
V0 α
so,
V (T ) ≈ V0 [1 + α(T − T0 )] . (42.7)
As one final point, we can apply the cyclic rule for partial derivatives to determine
the ratio καT :
¡ ∂V ¢ µ ¶
α ∂T P cyclic ∂P
= ¡ ∂V ¢ = (42.8)
κT − ∂P T rule ∂T V
This section is a review from the first semester with an additional example beyond
the ideal gas.
276
thus
µ ¶ ¶ µµ ¶ µ ¶
∂U ∂U ∂V ∂V
CP = + +P (42.12)
∂TV ∂V T ∂T P ∂T P
µ ¶ ∙µ ¶ ¸
∂V ∂U
= CV + +P .
∂T P ∂V T
¡ ∂U ¢ ¡ ∂P ¢
Recall the expression for internal pressure ∂V T
= T ∂T V
− P . Then
µ ¶ ∙ µ ¶ ¸
∂V ∂P
CP = CV + T / + P/
−P (42.13)
∂T P ∂T V
Finally µ ¶ µ ¶
∂V ∂P
CP = CV + T (42.14)
∂T P ∂T V
1. Explicit in P : Replace
µ ¶ ¡ ∂P ¢
∂V
with − ¡ ∂T
∂P
¢V (42.17)
∂T P ∂V T
2. Explicit in V : Replace
µ ¶ ¡ ∂V ¢
∂P ∂T P
with − ¡ ∂V ¢ (42.18)
∂T V ∂P T
277
Examples
278
42.3. Expansion of Gases
As we learned last semester the value of w depends on Pex during the expansion.
nRT
For an ideal gas (P = V
) this becomes
Z V2 µ ¶
nRT V2
−wrev = dV = nRT ln (42.27)
V1 V V1
Also recall that −wrev is the maximum possible work that can be done in an
expansion. −wrev = −wmax .
2. Adiabatic expansion q = 0.
Isothermal expansion
279
Adiabatic expansion
280
42.3.3. When P is the more convenient variable
/ dV/ + V dP
dH = dq + dw + P (42.34)
dH = V dP.
Now, µ ¶
∂H
CP = =⇒ dH = Cp dT = V dP (42.35)
∂T P
For an ideal gas this becomes
nRT
Cp dT = dP (42.36)
P
Going from (T1 , P1 ) to (T2 , P2 ):
Z T2 Z P2
CP nR
dT = dP. (42.37)
T1 T P1 P
If CP (T ) is reasonably constant over the internal T1 to T2 then this is approxi-
mately µ ¶ µ ¶
T2 P2
C̄P ln = nR ln (42.38)
T1 P1
where C̄P = 12 (CP (T1 ) + CP (T2 )) . Or, in terms of molar heat capacity
µ ¶ µ ¶
T2 P2
C̄P m ln = R ln (42.39)
T1 P1
281
So µ ¶ µ ¶
P2 C̄P m V2
ln =− ln (42.41)
P1 C̄V m V1
| {z }
≡γ
hence µ ¶ µ ¶ µ ¶ µ ¶γ
P2 V2 V1 V1
ln = −γ ln = γ ln = ln (42.42)
P1 V1 V2 V2
Thus µ ¶ µ ¶γ
P2 V1
= ⇒ P2 V2γ = P1 V1γ , (42.43)
P1 V2
but Pi Viγ are arbitrary so this implies P V γ = constant (** NOTE: The axes
should be reversed **)
Consider a gas expanding adiabatically against a vacuum (Pex = 0). In this case
q = 0 (adiabatic) and w = 0 (since −dw = Pex dV ).
282
This implies
4U = q + w = 0. (42.44)
¡ ∂T ¢
We want to find ∂V U
.
Identity: µ ¶ µ ¶ µ ¶ µ ¶
∂T ∂T ∂U 1 ∂U
=− = (42.45)
∂V U ∂U V ∂V T CV ∂V T
| {z }
1/CV
¡ ∂U ¢
For an ideal gas ∂V T = 0 (since U(T, V ) = U(T )). Thus in as much as the
¡ ∂T ¢
gas can be considered ideal ∂V U
= 0. That is, for Joule type expansion the
temperature of the gas does not change. For real gases this is not strictly equal
to zero.
283
The work done on the left is
Now,
4U = U2 − U1 = wL + wR = P1 V1 − P2 V2 (42.48)
Thus
U2 + P2 V2 = U1 + P1 V1 ⇒ H2 = H1 (42.49)
¡ ∂T ¢
We want to find ∂V H
≡ μ. (the Joule-Thomson coefficient).
Identity: µ ¶ µ ¶ µ ¶ µ ¶
∂T ∂T ∂H 1 ∂H
=− = =μ (42.50)
∂P H ∂H P ∂P T CP ∂P T
| {z }
1/CP
284
Recall the useful identity
µ ¶ µ ¶
∂H ∂V
=V −T (42.51)
∂P T ∂T P
Thus ¡ ¢
−V + T ∂V
∂T P
μ= (42.52)
CP
Example: The one term virial equation: (equation of state P V = nRT + nB)
µ ¶
1 −nRT nRT 0
μ = − nB + + nT B (42.53)
CP P P
−B + T B 0
μ = .
CP m
Limts:
285
43. Entropy of Gases
Entropy must be calculated along reversible paths. This is not a problem though
since entropy is a state function.
• At constant V :
dq=CV dT
— dU = dq + dw =⇒ dU = CV dT, but also dU = T dS. So
Z T2
CV CV
dS = dT =⇒ 4S = dT. (43.1)
T T1 T
P dq=C dT
— dH = dU +P dV +V dP = dq−P dV +P dV +V dP . So dH = dq =⇒
dq=T dS
dH = CP dT, but also dH = T dS. So
Z T2
CP CP
dS = dT =⇒ 4S = dT. (43.2)
T T1 T
286
286
• Using the equation of state
Z V2
nRdV nR V2
dS = =⇒ 4S = dV = nR ln . (43.3)
V V1 V V1
If two variables change in going from the initial to final states break the path into
two paths in which only one variable changes at a time.
• Since the gas is ideal, there are simply two separate equations:
VA + VB VB + VA
4SA = nA R ln , 4SB = nB R ln (43.5)
VA VB
and
4Smix = 4SA + 4SB (43.6)
287
• Recall Avogadro’s principle: n ∝ V for an ideal gas. So.
⎛ ⎞
⎜ nA + nB nB + nA ⎟
⎜ ⎟
4Smix = R ⎜nA ln + nB ln ⎟ = −R (nA ln XA + nB ln XB )
⎝ nA nB ⎠
| {z } | {z }
1/XA 1/XB
(43.7)
¡ ∂S ¢ ¡ ∂V ¢
Use Maxwell relation ∂P T
= − ∂T P
and single term viral equation, V =
nRT
P
+ nB.
So µ ¶ µ ¶
∂S ∂V nR
=− =− − nB 0 (43.8)
∂P T ∂T P P
Hence
µ ¶ U→
nR 0 P2
dS = − →
− nB dP =⇒ S2 − S1 = −nR ln − nB 0 (P2 − P1 ) (43.9)
P P1
For an ideal gas B 0 = 0, so
P2
S2ideal − S1ideal = −nR ln (43.10)
P1
Thus
S2 − S1 = S2ideal − S1ideal − nB 0 (P2 − P1 ) (43.11)
Letting P1 → 0 and P2 → P θ (Standard pressure 1 bar), this becomes
ideal ideal
S2 − /
S1 = S2ideal − /
S1 − nB 0 (P2 − P1 ) (43.12)
S(P θ ) = S θ − nB 0 P θ (43.13)
288
The entropy at any P and T can be obtained expresses as
Thus
P
S(T, P ) = S θ (T ) − nR ln − nB 0 P (43.15)
Pθ
289
Key Equations for Exam 3
Listed here are some of the key equations for Exam 3. This section should not
substitute for your studying of the rest of this material.
The equations listed here are out of context and it would help you very little to
memorize this section without understanding the context of these equations.
The equations are collected here simply for handy reference for you while working
the problem sets.
Equations
290
290
• The reaction velocity is
1 d[I]
v= (43.19)
vi dt
• The relation between the rate constant and the thermodynamic equilibrium
constant is
kf
Kc = (43.20)
kr
• The Arrhenious equation
Ea
k = Ae− RT (43.21)
4G = 4H − T 4S (43.22)
• Eyring’s equation is
kb T − 4G‡ kb T − 4H ‡ 4S‡
k= e RT = e RT e R (43.23)
h h
• Compressibility Factor:
PV P Vm
z= = . (43.25)
nRT RT
• The virial series is
µ ¶ µ ¶2 µ ¶3
1 1 1
z = 1 + B(T ) + C(T ) + D(T ) + ··· . (43.26)
Vm Vm Vm
CP m = CV m + R (43.27)
291
Part VIII
More Thermodyanmics
292
292
44. Critical Phenomena
The point on the top of the coexistence curve is called the critical point. It is
characterized by a critical temperature, Tc , and a critical density ρc .
293
293
44.1.1. Gas Laws in the Critical Region
The vapor pressure of a substance is taken from the gas laws as the pressures
where A1 = A2 in the above figure.
294
44.1.2. Gas Constants from Critical Data
Consider the van der Waals equation at the critical point (Pc , Tc , Vmc )
RTc a
Pc = − 2 . (44.1)
Vmc − b Vmc
dP 2
d P
There is an inflection point ( dVm
= 0, dV 2 = 0) at the critical point. So, setting
m
the first and second derivatives at the critical point equal to zero we get
¯
dP ¯¯ −RTc 2a
¯ = 2
+ 3 =0 (44.2)
dVm c (Vmc − b) Vmc
and ¯
d2 P ¯¯ 2RTc 6a
2 ¯ = 3
− 4 =0 (44.3)
dVm c (Vmc − b) Vmc
solving these three equations for Pc , Tc and Vmc gives
295
44.2. The Law of Corresponding States
One can define unitless “reduced” variables Tr = T /Tc , Pr = P/Pc , and Vr = V /Vc .
Then zr = PRT
r Vr
r
.
• (dAα )T = −P dVα − μα dn
• (dAβ )T = −P dVβ + μβ dn
= 0 since V is constant
z }| { ¡ ¢
• (dA)T,V = −P (dVα + dVβ ) + μβ − μα dn
When α, β denote liquid (or solid) and vapor phases, then for a given T , the
pressure of the system when μβ = μα is the called the vapor pressure of the
material at temperature T.
296
¡ ¢
For phase changes at constant T and P then (dG)T,P = μβ − μα dn. So again
μβ = μα is the condition for equilibrium.
Now, µ ¶
∂G
S=− (44.9)
∂T P,n
So, µ ¶ µ ¶
∂S ∂ ∂G ∂ ∂G ∂μ
=− =− =− . (44.10)
∂n P,T ∂n ∂T ∂T ∂n ∂T P
But S = nSm (T, P ) so, µ ¶
∂μ
= −Sm . (44.11)
∂T P
Similarly, µ ¶
∂μ
= Vm . (44.12)
∂P T
Now the total differential of μ is
−S V
z }|m¶ { µ
µ
m
z }| ¶{
∂μ ∂μ
dμ(T, P ) = dT + dP (44.13)
∂T P ∂P T
dμ(T, P ) = −Sm dT + Vm dP
297
44.3.2. The Clapeyron Equation
At equilibrium μβ = μα so,
Now
dP Smα − Smβ −4φ Sm 4S= 4H
T 4φ Hm
= = = (44.15)
dT Vmα − Vmβ −4φ Vm T 4φ Vm
This is the Clapeyron Equation
dP 4φ Hm
= (44.16)
dT T 4φ Vm
The above Clapeyron equation applies to any phase transition; consider the liquid-
vapor phase transition.
Now
4v V = Vm,vap − Vm,liq ' Vm,vap (44.17)
Assuming the vapor phase obeys the ideal gas equation of state,
RT
4v V = (44.18)
P
Substituting this into the Clapeyron equation gives
dP 4v Hm 4v Hm P
= RT
= (44.19)
dT T P RT 2
Collecting the T ’s on one side of the equation and the P ’s on the other we get
dP 4v Hm dT
= (44.20)
P R T2
dP dT
Now we identify P
= d(ln P ) and T2
= −d(1/T ) so this becomes
4v Hm
d(ln P ) = − d(1/T ) (44.21)
R
298
Rearranging again leads to
d(ln P ) 4v Hm
=− (44.22)
d(1/T ) R
Examples
• Solid—liquid
• Solid—solid
This can be rearranged so that terms independent of pressure (the standard chem-
ical potentials) are one side and the terms that depend of pressure are on the other
side
μª ª
α − μβ = (Vmβ − Vmα ) (P − P )
ª
(44.24)
299
Thus for any given T only one P allows for equilibrium.
Definitions
• Phase Diagram: A graph of P vs. T for a system which shows the lines
of equal chemical potential
• Triple Point: The point where all three phases coexist in equilibrium:
300
45. Transport Properties of Fluids
Transport properties of matter deal with the flow (or flux) of some property along
a gradient of some other property.
45.1. Diffusion
301
301
The flux of material through a plane depends on the concentration difference
dC 1 dn dC
J = −D =⇒ = −D
dx A dt dx
where D is the diffusion constant
1 dn dC
= −D (45.2)
A dt dx
This is Fick’s first law of diffusion (in one dimension).
302
The solution of this partial differential equation depends on the boundary condi-
tions. Numerous methods of solution exist for this equation but they are beyond
the scope of the course.
The solution for two special boundary conditions are of interest and will simply
be presented here without derivation
45.2. Viscosity
303
dv mass
The frictional (viscous) force is F = ηA dx . (The units of η are lenght·time
. 1 poise
g
= cm·s .)
Poiseuille’s Formula
• For a liquid flowing trough a tube (radius r, length l), the volume of flow
4V in time 4t is
4V πr4 4P
=− (45.8)
4t 8ηl
where 4P is the driving pressure, i.e., the difference in pressure on either
side of the tube.
• For a gas µ ¶
4V πr2 Pi2 − Pf2
= (45.9)
4t 16ηl P0
where Pi is the inlet pressure, Pf is the outlet pressure and P0 is the pressure
at which the volume is read.
304
• The frictional force (exerted upwards) is proportional to velocity: Ff = −fv.
Stokes showed f = 6πηr
4πr3
• Gravitational force (exerted downwards): Fg = 3
(ρ − ρ0 )g, where g is the
gravitational acceleration (9.8 m/s2 ).
4πr3
−f vterm + (ρ − ρ0 )g = 0 (45.10)
3
4πr3 (ρ − ρ0 )g
vterm =
3f
using f = 6πηr
/ r/3 (ρ − ρ0 )g 2r2 (ρ − ρ0 )g
4π
vterm = ¡ ¢ = (45.11)
3 6π / ηr
/ 9η
Consider a slab of solid material of area A between two large parallel plates a
distance D apart. The plates are held at constant but different temperatures T1
and T2 (T1 > T2 ) for a sufficiently long time that a steady state exists.
305
Under such conditions, a linear steady state temperature distribution across the
material is established. And a constant rate of heat flow dq
dt
is needed to maintain
the temperature difference 4T = (T1 − T2 )
1 dq 4T
= −κ . (45.13)
A dt D
If we take the limit where D becomes infinitesimally small (D → dx) we obtain a
differential form of this equation:
1 dq dT
= Qf = −κ , (45.14)
A dt dx
where Qf is the heat flux. This is called Fourier’s law of heat conduction
(one-dimensional version).
Thermal conductivities are positive quantities so Fourier’s law says that heat flow
down a temperature gradient, i.e., from hot to cold.
306
45.3.2. Thermal Conductivity of Solids
For the most part, the thermal conductivity of solids have to be determined ex-
perimentally because many factors contributing to the thermal conductivity are
difficult to predict.
In general metals are better heat conductors than nonmetals and crystals are
better heat conductors than amorphous materials.
The Wiedemann, Frantz and Lorenz equation relates the thermal conductivity to
electrical conductivity, κel for pure metals:
κ
= L = const. (45.15)
κel T
The Lorenz number is taken as constant because it is only a very weak function
of temperature with a change of 10 to 20% per 1000 degrees being typical.
The Wiedemann, Frantz and Lorenz equation breaks down at low temperature
because metals become superconductive. There is no analog to superconductivity
for thermal conductivity.
307
46. Solutions
Solutions are mixtures of two or more pure substances. So, in addition to the
parameters needed to characterize a pure substance, one also needs to keep track
of the amount of individual species in solution
n1
• mole ratio r = n2
n2
• mole fraction X2 = n1 +n2
, X1 = 1 − X2
1000X2
• molality m = M1 X1
, where M1 is the molecular weight of species 1
n2
• Molarity c2 = L solution
For example,
4mix V = Vsoln − Vsolute − Vsolvent (46.2)
308
308
In general, it is a function of T, P, n1 and n2 : V (T, P, n1 , n2 ). So, the total
derivative is
µ ¶ µ ¶ µ ¶ µ ¶
∂V ∂V ∂V ∂V
dV = dT + dP + dn1 + dn2 ,
∂T P,n1 ,n2 ∂P T,n1 ,n2 ∂n1 T,P,n2 ∂n2 T,P,n1
³ ´ (46.3)
∂V
∂ni
≡ V̄i , the partial molar volume.
T,P,nj
Similarly
µ ¶ µ ¶ µ ¶ µ ¶
∂G ∂G ∂G ∂G
dG = dT + dP + dn1 + dn2 ,
∂T P,n1 ,n2 ∂P T,n1 ,n2 ∂n1 T,P,n2 ∂n2 T,P,n1
³ ´ (46.4)
∂G
∂ni
≡ μi .
T,P,nj
So now for the more general case of mixtures the chemical potential of a species
of the partial molar free energy for that species, rather than simply the molar free
energy as it was earlier.
46.2.1. Notation
The study of solutions brings with it a large number of symbols which we collect
here for future reference.
Material
Pure liquid i Vi• Hi• Si• G•i
• • •
Pure liquid i per mole Vmi Hmi Smi μ•i
Whole solution V H S G
Solution/(total moles) Vm Hm Sm Gm
Partial molar of i in solution V̄i H̄i S̄i μi
Apparent molar (of solute) φ V φ
H
Reference state Viª Hiª Siª μª
i
309
46.2.2. Partial Molar Volumes
So, U
¡ ¢ dλ
dV = V̄1 n1 + V̄2 n2 dλ =⇒ V = V̄1 n1 + V̄2 n2 (46.7)
That is, the total volume of the solution is equal to the sum of the partial molar
volumes each weighted by their respective number of moles.
The total volume, however, is not necessarily the mole weighted sum of the vol-
umes of each component in its pure (unmixed) state. More specifically
• •
4mix V = V − (Vm1 n1 + Vm2 n2 ) (46.8)
¡ ¢ • •
= V̄1 n1 + V̄2 n2 − (Vm1 n1 + Vm2 n2 )
¡ •
¢ ¡ •
¢
= V̄1 − Vm1 n1 + V̄2 − Vm2 n2
1. one unit of baseballs are mixed with one unit of basketballs. 4mix V < 0.
2. one unit of baseballs are mixed with one unit of books. 4mix V > 0.
310
46.3. Reference states for liquids
Recall that activity gives a measure of the deviation of the real state from some
reference state
311
Also recall that the mathematical definition of activity ai of some species i is
implicitly stated as
ai
limª =1 (46.9)
ζ→ζ g(ζ)
where g(ζ) is any reference function (e.g., pressure, mole fraction, concentration
etc.), and ζ ª is the value of ζ at the reference state.
This implicit definition is awkward so for convenience one defines the activity
coefficient as the argument of the above limit,
ai
γi ≡ (46.10)
g(ζ)
Connecting with the chemical potential we saw last semester that the deviation
of the chemical potential at the state of interest versus at the reference state is
determined by the activity at the current state (the activity at the reference state
is unity by definition).
μi − μª
i = RT ln ai . (46.12)
In discussing both Raoult’s law and Henry’s law, we are describing the behavior
of a liquid solution by measuring the vapor (partial) pressures of the components
312
For simplicity we consider here only a two component solution.
dG = (μ1 n1 + μ2 n2 ) dλ (46.14)
then
G = μ1 n1 + μ2 n2 . (46.15)
Recall that
4mix G = G(soln) − G(pure components) (46.16)
Hence,
Now,
ai low P Pi
μ1 − μ•1 = RT ln •
' RT ln • , (46.18)
ai Pi
where Pi is the vapor pressure of the ith component above the solution.
313
Thus µ ¶
a1 a2
4mix G = RT n1 ln • + n2 ln • (46.19)
a1 a2
or at low P µ ¶
P1 P2
4mix G = RT n1 ln • + n2 ln • (46.20)
P1 P2
Raoult’s Law:
Pi = Xi Pi• (46.21)
That is, the vapor partial pressure of a component of a mixture is equal to the
mole fraction of the component times the vapor pressure that the component
would have if it were pure.
The change in free energy upon mixing for solutions ideally obeying Raoult’s law
is à !
id(RL) X1 P/1• X2 P/2•
4mix G = RT n1 ln + n2 ln (46.22)
P/1• P/2•
id(RL)
4mix G = RT (n1 ln X1 + n2 ln X2 ) (46.23)
Again, this is for an ideal solution in the Raoult’s Law sense.
From µ ¶ µ ¶
∂G ∂ (G/T )
S=− and H = − , (46.24)
∂T P ∂ (1/T ) P
the entropy of mixing for an ideal Raoult solution is
id(RL)
4mix S = −R (n1 ln X1 + n2 ln X2 ) (46.25)
314
(since G/T is independent of 1/T ).
Let us apply the definition of activity for the Raoult’s law reference state.
So,
(RL)
ai
lim =1 (46.27)
Xi →1 Xi
implies
(RL) (RL)
ai = γi Xi , (46.28)
(RL)
and γ i → 1 as Xi → 1
Raoult’s law is a purely statistical law. It does not require any kind of interaction
among the constituent particle making up the solution.
Since, in reality, there are specific interactions between particles, real solutions
generally deviate from Raoult’s law.
315
It is very important to note that this deviation from Raoult’s law is a property of
the solution and NOT any given component.
For example, for a given component, mixing with one substance may lead to
a positive deviation but mixing with another substance may lead to a negative
deviation.
Henry’s Law:
Pi = kXi Xi , (46.29)
Henry’s law applies to the solute not to the solvent and becomes more correct for
real solution as the concentration of solute goes to zero (Xi → 0), i.e., at infinite
dilution.
316
The Reference State (HL)
Referring to the definition of activity again we see that the reference function is
g(ζ) = ζ = Xi . and the reference state is now Xi = 0
So,
(HL)
ai
lim =1 (46.31)
Xi →0 Xi
implies
(HL) (HL)
ai = γ i Xi , (46.32)
(HL)
and γ i → 1 as Xi → 0
If instead of mole fraction, molality or molarity is used then
(HL)
ai = γ (HL)
mi mi (46.33)
and
(HL) (HL)
ai = γ Mi Mi (46.34)
respectively.
Both Raoult’s law and Henry’s law become better approximations for real solu-
tions as the solution becomes pure. But, they apply to opposite species in the
solution. Raoult’s law applies to the dominant species, X1 → 1, whereas Henry’s
law applies to the subdominant species X2 → 0. So, in summary
• Raoult’s law: γ 1 → 1 as X1 → 1
• Henry’s law: γ 2 → 1 as X2 → 0
317
46.4. Colligative Properties
• Osmotic pressure
We will consider the examples of freezing point depression and osmotic pressure
318
Using the Raoult’s law reference state (since we are interested in the behavior of
the dominant species), μ1 (soln) = μ•1 + RT ln a1 :
For small changes in the freezing point we may approximate T by Tf• in the
integrand. So, Z Tf
4f H −4f H
ln a1 ' •2
dT = Θ, (46.38)
Tf• RTf RTf•2
where Θ ≡ Tf• − Tf . The freezing point depression is
RTf•2 ln a1
Θ=−
4f H
319
In the above figure μ1 (left) = μ1 (right), hence
where V̄1 is the partial molar volume of the solvent in solution (difficult to measure)
and Π is the hydrostatic (osmotic) pressure.
X22 X23
ln(1 − X2 ) = −X2 + − − · · · ' −X2 , (46.42)
2 3
n2 n2
but X2 = n1 +n2
' n1
for dilute solutions. Thus
1 V•
z }| {
• •
n2 Vm1 Π n1 Vm1 Π
' =⇒ n2 ' , (46.43)
n1 RT RT
320
or,
n2
Π= RT = cRT, (46.44)
V1•
|{z}
'c
Note the similarity of this equation with the ideal gas equation: P = cRT. Thus
the solute in a very dilute solution behaves as if it were an ideal gas.
321
47. Entropy Production and
Irreverisble Thermodynamics
We have seen that thermodynamics tells us if a process will occur and kinetics
tells us how fast a process will occur.
The main concept of this approach is the idea of entropy production and, ulti-
mately, entropy production per unit time–how fast we are producing entropy.
47.1. Fundamentals
We know the difference between reversible and irreversible processes from before.
However, we will state their respective definitions here in a manner best suited
for this chapter.
322
322
Reversible process: dynamical equations are invariant under time inversion
(t → −t).
Irreversible process: dynamical equations are not invariant under time inver-
sion (t → −t).
1 ∂T ∂ 2 T t→−t 1 ∂T ∂ 2T 1 ∂T ∂2T
= =⇒ = =⇒ − = , (47.2)
κ ∂t ∂x2 κ ∂(−t) ∂x2 κ ∂t ∂x2
We will be concerned with the change in entropy, dS, which can be split into two
components dS = de S + di S.
Definitions
323
Splitting up dS into these two parts permits an easy discussion of both open and
isolated systems–the difference between the two appearing only in de S.
• di S = 0 (reversible change)
As you might expect, the second law underlies all the concepts of this chapter.
This is simply another in our long list of alternative statements of the second law.
324
I
II
Considering the above figure of an isolated system, we write the principle of Clau-
sius as
dS = dS I + dS II ≥ 0. (47.3)
di S I ≥ 0 and di S II ≥ 0 (47.4)
¡ ¢
and the possibility of, for example, di S I < 0 and di S II > 0 such that di S I + S II >
0 is excluded.
47.3. Examples
The idea of entropy production can be applied to any of the processes we have
talked about; mixing, phase changes, heat flow, chemical reactions, etc. As exam-
ple we now consider the last two of these: heat flow and chemical reactions.
325
47.3.1. Entropy Production due to Heat Flow
Recall from the lecture on transport phenomena that the heat flux Qf is given by
4T
Qf = −κ (47.5)
D
q
We are now interested in exposing the time dependence, so, using Qf = 4t
we get
q κA4T
=− (47.6)
4t D
in differential form this is
dq dT
= −κA . (47.7)
dt dx
Example: Find the entropy production in a system consisting of two identical
connected blocks of metal (I and II), one of which is held at temperature T1 and
the other at T2 (take T1 > T̄ > T2 ) where T̄ is the temperature at the interface.
326
Considering the whole system
ed S i dS
z }| { z }| {
dqI dqII de qI de qII di qI di qII
dS = + = + + + . (47.8)
T1 T2 T1 T2 T1 T2
The quantity de qj is the amount of heat supplied by the environment to hold block
j at its fixed temperature.
Furthermore the heat going out of I through the connecting wall is equal to the
heat coming into II through the connecting wall:
di S
To do so we must consider the entropy production per unit time dt
.
327
For this example µ ¶
di S di qI 1 1
= −
dt dt T1 T2
From chapter 24 we know
di qI −Aκ4T
= . (47.11)
dt D
So, µ ¶
di S −Aκ4T 1 1
= − (47.12)
dt D T1 T2
To determine T̄ we use the fact that the heat flow out of I is equal to the heat
flow into II:
di qI −di qII
= . (47.13)
dt dt
Using the above expression for heat flow gives us T̄ since,
/ ¡
/κ A ¢ / ¡
/κ A ¢ T1 + T2
− T1 − T̄ = − T̄ − T2 ⇒ T̄ = ; (47.14)
/
D /
D 2
Definitions:
P
1. Chemical affinity: a ≡ − (4rxn G)T,P = − i vi μi and a ≡ − (4rxn A)T,V =
P
− i vi μi
328
• e.g., for the reaction N2 + 3H2 → 2NH3
dnN2 dnH2 dnNH3
dξ = = = (47.15)
(−1) (−3) (2)
and
a = 2μNH3 − μN2 − 3μH2 (47.16)
dξ
The connection to kinetics: reaction rate v = dt
but
−adξ
dq z }| {
z }| { dq (dA) T,V
(dA)T,V = (dU)T,V − T dS ⇒ dS = − (47.18)
T T
so
ed S i dS
z}|{ z}|{
dq adξ
dS = + (47.19)
T T
The entropy production per unit time for a chemical reaction is a function of both
the chemical affinity and of the reaction rate
di S a dξ a
= = v≥0 (47.20)
dt T dt T
We see that for a spontaneous process the entropy production per unit time is
positive. This is because a = − (4rxn A)T,V is positive as is v.
329
Simultaneous Reactions
For N simultaneous chemical reactions, the entropy production per unit time
generalizes to
1X
N
di S
= aj vj ≥ 0. (47.21)
dt T j=1
The second law requires that the total entropy production for simultaneous reac-
tions is positive. It says nothing about the entropy production of the individual
component reactions other then the sum of all the component entropy productions
must be positive.
For example in a system of two coupled reactions we could have a1 v1 < 0, a2 v2 > 0
such that a1 v1 + a2 v2 > 0.
That is, diffusion is the flux of matter down a concentration gradient. The so-
called Soret effect is flux of matter down a temperature gradient. Conversely, the
so-called Dufour effect is heat flux down a concentration gradient
330
The following table lists a number of thermodynamically coupled phenomena
If the perturbation is released the system will begin to evolve in time as it heads
back towards the thermalized equilibrium state.
• Reversibly
• Irreversibly
331
• A strong signal is seen because all the spinning nuclei cooperate.
• Dephasing causes a decrease in the observed signal because now not all nuclei
are cooperating.
• Now a radio pulse with the opposite phase is applied to make the nuclei spin
in the opposite direction
• This undoes or reverses the dephasing process and the signal regains strength
• The full signal is not recovered however since all the while random ther-
malization is taking place to irreversibly destroy the coherence among the
nuclei.
332
Key Equations for Exam 4
Listed here are some of the key equations for Exam 4. This section should not
substitute for your studying of the rest of this material.
The equations listed here are out of context and it would help you very little to
memorize this section without understanding the context of these equations.
The equations are collected here simply for handy reference for you while working
the problem sets.
Equations
d(ln P ) 4φ Hm
=− (47.23)
d(1/T ) R
333
333
• Fick’s second law of diffusion:
∂C ∂ 2C
=D 2. (47.25)
∂t ∂x
• Relation between the viscosity and the diffusion constant:
kT f =6πηr kT
D= = . (47.26)
f 6πηr
• Chemical potential
μ = μª + RT ln a (47.29)
• Raoult’s Law:
Pi = Xi Pi• (47.30)
• Henry’s Law:
Pi = kXi Xi . (47.32)
where kXi is the Henry’s law constant,
µ ¶
Pi
kXi = lim . (47.33)
Xi →0 Xi
334
Index
335
335
Clapeyron equation 298, 300, 333 nuclear-nuclear potential energy
Clausius-Clapeyron equation 299, operator for 61
333 Schrodinger equation for 62
coefficient of thermal expansion 274 Dieterici gas 270
coexistence curve 293 diffusion 301
colligative properties 318 diffusion constant 302
commutator 30, 189 eigenfunction 5
completeness 191 eigenvalue 5
complimentary variables 30 eigenvalue equation 190
compressibility factor electric dipole approximation 79, 231
at the critical point 295 electrolytes
compressibilty factor 270, 291 strong 161
configuration 90 electrophoretic effect 167
confluent hypergeometric functions elementary reactions 255
65 and stoichiometry 256
correspondence principle 41 molecularity 256
critical point 300 emission spectroscopy 241
cyclic rule 14, 108 enemble 89
cylindrical symmetry 69 ensemble average 103, 132
Debye—Huckel limiting law 164, 178 enthalpy 136
Debye—Huckel theory 163 entropy 105
Debye—Huckel—Guggenheim equation change for changes in temper-
164 ature 286
Debye’s law 129, 133 change for isothermal expansion
degeneracy 186 286
of the ensemble 98 change for mixing 287
diathermic wall 120 of real gases 288
diatomic molecules entropy production 322, 323
electron-electron potential en- due to chemical reactions 328
ergy operator for 61 due to heat flow 326
electronic kinetric energy oper- equation of state 116
ator for 61 for a Berthelot gas 118
electronic wavefunction for 62 for a Dieterici gas 118
Hamiltonian for 61 for a Redlich—Kwang gas 118
nuclear kinetic energy operator for a van der Waals gas 117
for 61 for an ideal gas 116
nuclear-electron potential energy for gases 269
operator for 61 equilibrium constant 135
336
equlibrium constant 153 classical 27
Euler’s identity 4 harmonic oscillator 38
expansion energy levels for 40, 44, 86
of gases 111 potential energy 39
reversible 114 Schrodinger equation for 39
extent of reaction 328 heat 109
Eyring’s equation 265, 291 sign convention 110
fermions 56 heat capacity 115, 133
Fick’s first law 302, 333 Heisenberg uncertainty principle 30
Fick’s second law 302, 334 and the harmonic oscillator 41
first law of thermodynamics 121, helium 55
133 electron-electron repulsion term
flipping coins 90 55
fluctuation 92 Hamiltonian 55
fluorescence 242 Helmholtz free energy 106
stokes shift 242 Henry’s law 311, 316, 334
Fourier’s law of heat conduction 306, Henry’s law constant 316, 334
334 Hermite polynominals 40
Franck—Condon integral 243 hot bands 66
Franck—Condon principle 243 Hund’s rule 205
free energy hydrogen atom
Gibbs 138 ioniztion energy of 19
Helmholtz 137 hydrogen molecule 74
fugacity 147 hydrogenic systems 46
fundamental transistions 66 energy levels for 49, 86
general equlibrium 151 Hamiltonian 47
generalized displacement 110 normalization constant 49, 85
generalized force 110 potential energy for 47
gerade 69 Schrodinger equation for 47
Gibb’s free energy 106 wavefunction (no spin) 49
Gibbs-Duhem equation 163 wavefunction (with spin) 52
good theory 16 ideal solution
group Raoult’s law 314
mathematical definition of 222 immiscible solutions 153
multiplication table 223 infrared spectroscopy 66
group theory 221 internal energy 103, 121
Hamiltonian operator 27 intramolecular vibrational relaxation
Hamitonian (IVR) 242
337
inversion symmetry 69 molecular hydrogen ion 67
operator 69 Hamiltonian for 67
ion mobility 166 molecular orbital diagram 76
and current 168 molecular orbitals 68
ion transfer 174 molecular rotations 235
IR spectroscopy 231 asymmetric tops 239
and the character table 232 centrifugal stretching 236
isothermal compressibility 274 linear tops 238
isothermal expansion 279 polyatomic molecules 237
Joule expansion 282 spherical tops 239
Joule-Thomson expansion 283 symmetric tops 238
kinetic theory of gases 250 vibrational state dependence of
Lagrange multipliers 95 236
Laguerre polynominals 49 molecular vibrations 228
laminar flow 304 molecule
law of corresponding states 296 Scrodinger equation for 78
law of rectilinear diameters 293 momentum operator 5
Legendra polynomials 200 Morse oscillator 64
linear combinations of atomic or- energy levels for 65, 86
bitals (LCAO) 72 Schrodinger equation for 65
Lorenz number 307 wavefunction for 65
many electron atom Morse potential 64, 86, 240
Hamlitonian for 59 force constant associated with
maximal work 113 9
Maxwell relations 140 Taylor series expansion of 8
Maxwell’s distribution of speeds 252, normal modes 229
290 operator
mean free path 253, 290 Hermitian 189
mean ionic activity 162 ladder 195
mean ionic activity coefficient 162 linear 189
method of initial velocities 259 symmetry 222
method of isolation 259 operator algebra 187
microstate 90 orientation quantum number 53
Mie scattering 84 orthogonality 191
mirror plane symmetry 70 overtone transitions 66
molar heat capacity 115 parameters
molecular collisions extensive 109
simple model for 252 intensive 109
338
particle in a box 31, 181 Poiseuille’s formula 304
energy levels 183 polarizability 79
energy levels for 34, 44, 218 postulate I (of quantum mechan-
features of the energy levels 35 ics) 22
normalization constant for 33 postulate II (of quantum mechan-
potenial energy 31 ics) 24
Schrodinger equation for 32 postulate III (of quantum mechan-
three dimensional 183 ics) 25
three dimensional energy levels pressure 104
185 principle of Clausius 125, 324
three dimensional wavefunction principle quantum number 52
185 probability amplitude 22
wavefunction for 183 probability distribution 22
wavefunctions for 34, 44, 218 PV work 111, 133
particle on a ring 194 Raman scattering 80
boundary conditions 194 Raman spectroscopy 66, 233
energy levels for 195, 218 and the character table 234
Hamitonian for 194 Raoult’s law 311, 312, 314, 334
wavefunctions for 195, 218 deviations from 315
partition coefficient 154 reference state 315
and drug delivery 155 rate law 255
for the Born model 174 rate laws 254
partition function determination of 258
canonical 96, 131 integrated 259
electronic 101 Rayleigh scattering 80
grand canonical 97 Rayleigh scattering law 81, 82, 87
isothermal—isobaric 97 reaction velocity 255, 291
microcanonical 96 reciprocal rule 108
molecular 100 red sunsets 82
rotational 101, 132 Redlich-Kwang gas 270
translational 101, 132 reference states 147
vibrational 101, 132 relationship between CP and CV
Pauli exclusion principle 56 139, 276
consquences of 58 relaxation effects 167
perturbation theory 207 rigid rotor 200
example of the quartic oscilla- degeneracy of 235, 248
tor 208 energy 235, 247
phase diagram 300 rotational energy levels 200, 219
339
degeneracy of 200 types of 108
rotational Hamiltonian 200 temperature 115
rule of mutual exclusion 234 term symbols 204
Rydberg constant 20 thermal conductivity 301
SATP 120 of gases 306
Schrodinger equation of liquids 306
time dependent 214 thermal equilibrium 120
time independent 27 third law of thermodynamics 128,
second law 133
“local” formulation 324 tips for solving problems 2
second law of thermodynamics 126, total derivative 107
133 transfer matrix 11
statements of 127 triple point 300
simple collision theory 262 two level system 211
Slater determinant 58 ‘left’ and ‘right’ states 213, 219
for lithium 59 Hamiltonian for 212
solar system model 17 Tyndall scattering 84
solvation 169 ungerade 69
solvophobic effect 176 van der Waals equation
specific heat 115
spherical harmonic functions 48, 200
spin 201
quantum number 51, 53
wavefunction 51
spin orientation
quantum number 51, 53
spin-orbit
coupling 205
Hamiltonian 205
interaction energy 205
spontaneous process 142
state function 121
table of important ones 136
Sterlings approximation 92
Stoke’s law 167, 304
STP 120
superposition 191
systems
340