This document discusses statistical thermodynamics and the partition function. It introduces the concept of microscopic configurations and their weights. The Boltzmann distribution relates the probability of a configuration to its weight, which depends on the energy levels and temperature. The partition function allows calculating thermodynamic properties like internal energy, entropy, and heat capacity from knowledge of the energy levels and degeneracies alone. It provides a statistical mechanical approach to thermodynamics.
Implication of Nernst's Heat Theorem and Its application to deduce III law of thermodynamics and Determination of absolute entropies of perfectly crystalline solids using III law of thermodynamics
Implication of Nernst's Heat Theorem and Its application to deduce III law of thermodynamics and Determination of absolute entropies of perfectly crystalline solids using III law of thermodynamics
lecture slide on:
Gibbs free energy and Nernst Equation, Faradaic Processes and Factors Affecting Rates of Electrode Reactions, Potentials and Thermodynamics of Cells, Kinetics of Electrode Reactions, Kinetic controlled reactions,Essentials of Electrode Reactions,BUTLER-VOLMER MODEL FOR THE ONE-STEP, ONE-ELECTRON PROCESS,Current-overpotential curves for the system, Mass Transfer by Migration And Diffusion,MASS-TRANSFER-CONTROLLED REACTIONS,
First part of Statistical Thermodynamics includes: Introduction, Ensembles, Types of Ensembles, Thermodynamic Probability, Boltzmann Distribution, Lagrange's Undetermined Multipliers, Partition Function, Types of Partition Functions, Thermodynamic Properties in terms of partition Function, Heat Capacity, Heat Capacity of Monoatomic Solids, Dulong-Petit law, Einstein Model for solids, 3rd Law and Residual Entropy
The postulates of quantum mechanics have been successfully used for deriving exact solutions to Schrodinger equation for problems like A particle in 1 Dimensional box Harmonic oscillator Rigid rotator Hydrogen atom • However for a multielectron system, the SWE cannot be solved exactly due to inter-electronic repulsion terms.
The SWE is solved by method of seperation of variables.
• However, the inter-electronic repulsion term cannot be solved because the variables cannot be seperated and the SWE cannot be solved. • Approximate methods have helped to generate solutions for such and even more complex real quantum systems. • Approximate methods have been developed for solving Schrodinger equation to find wave function and energy of the complex system under consideration. • Two widely used approximate methods are, 1. Perturbation theory 2. Variation method
Perturbation theory is an approximate method that describes a complex quantum system in terms of a simpler system for which the exact solution is known. • Perturbation theory has been categorized into, i. Time independent perturbation theory, proposed by Erwin Schrodinger, where the perturbation Hamiltonian is static. ii. Time dependent perturbation theory, proposed by Paul Dirac, which studies the effect of time dependent perturbation on a time independent Hamiltonian H0.
PERTURBATION THEOREM
FIRST ORDER PERTURBATION THEORY
FIRST ORDER ENERGY CORRECTION
FIRST ORDER WAVE FUNCTION CORRECTION
APPLICATIONS OF PERTURBATION METHOD
SIGNIFICANCE OF PERTURBATION METHOD
Reference,
https://en.wikipedia.org/wiki/Term_symbol
James E. Huheey, Ellen A. Keiter, Richard L.Keiter and Okhil K. Medhi, Inorganic Chemistry, Principles of Structure and Reactivity. 4th Edn. Pearsons
lecture slide on:
Gibbs free energy and Nernst Equation, Faradaic Processes and Factors Affecting Rates of Electrode Reactions, Potentials and Thermodynamics of Cells, Kinetics of Electrode Reactions, Kinetic controlled reactions,Essentials of Electrode Reactions,BUTLER-VOLMER MODEL FOR THE ONE-STEP, ONE-ELECTRON PROCESS,Current-overpotential curves for the system, Mass Transfer by Migration And Diffusion,MASS-TRANSFER-CONTROLLED REACTIONS,
First part of Statistical Thermodynamics includes: Introduction, Ensembles, Types of Ensembles, Thermodynamic Probability, Boltzmann Distribution, Lagrange's Undetermined Multipliers, Partition Function, Types of Partition Functions, Thermodynamic Properties in terms of partition Function, Heat Capacity, Heat Capacity of Monoatomic Solids, Dulong-Petit law, Einstein Model for solids, 3rd Law and Residual Entropy
The postulates of quantum mechanics have been successfully used for deriving exact solutions to Schrodinger equation for problems like A particle in 1 Dimensional box Harmonic oscillator Rigid rotator Hydrogen atom • However for a multielectron system, the SWE cannot be solved exactly due to inter-electronic repulsion terms.
The SWE is solved by method of seperation of variables.
• However, the inter-electronic repulsion term cannot be solved because the variables cannot be seperated and the SWE cannot be solved. • Approximate methods have helped to generate solutions for such and even more complex real quantum systems. • Approximate methods have been developed for solving Schrodinger equation to find wave function and energy of the complex system under consideration. • Two widely used approximate methods are, 1. Perturbation theory 2. Variation method
Perturbation theory is an approximate method that describes a complex quantum system in terms of a simpler system for which the exact solution is known. • Perturbation theory has been categorized into, i. Time independent perturbation theory, proposed by Erwin Schrodinger, where the perturbation Hamiltonian is static. ii. Time dependent perturbation theory, proposed by Paul Dirac, which studies the effect of time dependent perturbation on a time independent Hamiltonian H0.
PERTURBATION THEOREM
FIRST ORDER PERTURBATION THEORY
FIRST ORDER ENERGY CORRECTION
FIRST ORDER WAVE FUNCTION CORRECTION
APPLICATIONS OF PERTURBATION METHOD
SIGNIFICANCE OF PERTURBATION METHOD
Reference,
https://en.wikipedia.org/wiki/Term_symbol
James E. Huheey, Ellen A. Keiter, Richard L.Keiter and Okhil K. Medhi, Inorganic Chemistry, Principles of Structure and Reactivity. 4th Edn. Pearsons
Space lattice, Unit cell, Bravais lattices (3-D), Miller indices, Lattice planes, Hexagonal closed packing (hcp) structure, Characteristics of an hcp cell, Imperfections in crystal: Point defects (Concentration of Frenkel and Schottky defects).
X – ray diffraction : Bragg’s law and Bragg’s spectrometer, Powder method, Rotating crystal method.
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Fi ck law
Diffusion: random walk of an ensemble of particles from region of high “concentration” to region of small “concentration”.
Flow is proportional to the negative gradient of the “concentration”.
UCSD NANO 266 Quantum Mechanical Modelling of Materials and Nanostructures is a graduate class that provides students with a highly practical introduction to the application of first principles quantum mechanical simulations to model, understand and predict the properties of materials and nano-structures. The syllabus includes: a brief introduction to quantum mechanics and the Hartree-Fock and density functional theory (DFT) formulations; practical simulation considerations such as convergence, selection of the appropriate functional and parameters; interpretation of the results from simulations, including the limits of accuracy of each method. Several lab sessions provide students with hands-on experience in the conduct of simulations. A key aspect of the course is in the use of programming to facilitate calculations and analysis.
Stationary Quantum State: introduced by Niels Bohr, 1913:
A property of a stationary quantum state of a physical system of constant
energy is that probability to find a particle in any element of volume is
independent of the time. A stationary quantum state may be defined as a
condition of a system such that all observable physical properties are
independent of the time.
Stationary Quantum State: introduced by Niels Bohr, 1913:
A property of a stationary quantum state of a physical system of constant energy is that probability to find a particle in any element of volume is independent of the time. A stationary quantum state may be defined as a condition of a system such that all observable physical properties are independent of the time.
1. CY1001 T. Pradeep
Quantum Classical
Various forms of energies.
Everything turns out to be controlled by temperature
Statistical thermodynamics
Lectures 7, 8
Ref. Atkins 9th edition
Alberty, Silbey, Bawendi 4th edition
Energy levels Bulk properties
2. Need for statistical thermodynamics
Microscopic and macroscopic world
Energy states
Distribution of energy - population
Principle of equal a priori probabilities
Configuration - instantaneous
n1, n2,…molecules exist in states with energies ε0, ε1,…
N is the total number of molecules
{N,0,0,…} and {N-2, 2,0,…} are configurations
Second is more likely than the first
{1,1}, {2,0}, {0,2}
Weight of a configuration = how many times
the configuration can be reached.
0
ε
Reference to zero
Fluctuations occur
3. Energy
0
A configuration {3,2,0,0,..} is chosen in 10 different ways - weight of a configuration
How about a general case of N particles ? {n0,n1,…..} configuration of N particles.
A configuration {N-2,2,0,0,…}
First ball of the higher state can be chosen in N ways, because there are N balls
Second ball can be chosen in N-1 ways as there are N-1 balls
But we need to avoid A,B from B,A.
Thus total number of distinguishable configurations is, ½ [N(N-1)]
W = N!
W is the weight of the configuration.
How many ways a configuration can be achieved.
n0!n1!n2!....
1 2 3 4 5 6 7 8 9 10
N! ways of selecting balls (first ball N, second (N-1), etc.)
n0! ways of choosing balls in the first level. n1! for the
second, etc.
Distinct ways,
Generalized picture of weight
4. ln W = ln N!
n0! n1! n2!...
= ln N!- ln(n0! n1! n2!..)
=ln N! -(ln n0! +ln n1! +ln n2! + ...)
=ln N! -Σiln ni!
ln x!≈ x ln x-x Stirling’s approximation
ln W = (N ln N - N) - Σi (ni ln ni – ni) = N ln N –Σini ln ni
We have used, Σi ni = N
Better to use natural logarithm
5. Ni
N
= e -βε
i
Σi e -βε
i
β = 1
kT
Which is the dominating configuration having
maximum weight?
Generalized approach is to set dW = 0
There are problems as any configuration is not valid.
1. Energy is constant. Σi Ni εi = E
2. Constant number of molecules. Σi Ni = N
Boltzmann distributionPopulations in the
configuration of greatest
weight depends on the
energy of the state.
i is a sum over available states
W
Ni
Temperature gives the most probable populations
6. pi = e -βε
i
q
q =Σ levels l gl e-βε
i
q =Σi e -βε
i
lim T→0 q = g0
lim T→ ∞ = ∞
There are several ways of looking at i
How to look at partition functions?
Look at limiting cases
1. Partition function is the number of available states.
2. Partition function is the number of thermally accessible states.
3. How molecules are ‘partitioned’ into available states.
How to look at thermodynamic properties?
Molecular partition function
Because, ε0 = 0
For all higher levels ε is finite.
e-βε =1. Because, e-x is 0 when x is ∞.
Boltzmann distribution – population,
All terms will reduce to 1.
e-x is 1 when x is 0When number of states is finite,
we will not get ∞.
Another form of q:
7. Evaluation of molecular partition function
1 + x + x2 + x3 + ….= 1/(1-x)
q = 1 + e –βε + e –2βε + e –3βε +…= 1 + e –βε + (e –βε)2 + (e –βε)2 +…=1/(1- e –βε)
Fraction of molecules in energy levels is,
pi = e –βε
i/q = (1- e –βε) e –βε
i
Discussion of figure, next slide
For a two level system,
po = 1/(1 + e –βε)
p1= e –βε/q = e –βε/ (1+ e –βε)
As T à ∞, both po and p1 go to ½.
p
ε
0
ε
2ε
Consequences?
9. qx = 2╥ m
h2β X
1/2
En = n2h2
8 mX2 n =1,2….
εn = (n2-1)ε ε =
h2
8mX2
qx = Σ∞
n=1 e -(n2-1)βε
qx = ∫∞
1 e -(n2-1)βε dn energy levels are close, sum becomes an integral
qx = 1
βε
1/2
∫0
∞ e -x2dx = 1
βε
1/2 ╥ 1/2
2 =
2╥m
h2β
1/2
X
Approximations: Partition functions are often complex. Analytical expressions
cannot be obtained in several cases. Approximations become very useful.
For example, partition function for one dimensional motion
No big difference, if we take the lower limit to 0 and replace n2-1 to n2.
Substitute, x2 = n2βε, meaning dn = dx/(βε)1/2
Substitute for ε
Lowest energy level
has an energy of
h2
8mX2
Energy with respect
to this level is,
10. q =Σ all n e –βε(X)
n1
–βε(Y)
n2
-βε(Z)
n3
= Σn1 e- βε(X)
n1 Σn2 e -βε(Y)
n2 Σn3e -βε(Z)
n3
= qxqyqz
q =
2╥m
h2β
3/2
XYZ
q = V
Ʌ3
Ʌ = h
β
2╥m =
h
(2╥mkT)
1/2
1/2
Ʌ has dimensions of length,
thermal wavelength
J =kg m-2 s-2
εn1n2n3 = εn1
(X) + εn2
(Y) +εn3
(Z) Energy is a sum of independent terms
Independent motion in three dimensions
Question: How many more quantum states will be accessible for 18O2 compared to
16O2, if it were to be confined in a box of 1 cm3?
11. E = - N
q
Σi
d
dβ
e –βεi =-N
q
d
dβ
Σie-βεi=
N
q
dq
dβ
U = U(0) + E
U = U(0)- N
q
∂q
∂β v
U = U(0)- N ∂lnq
∂β v
E = Σi niεi
E =
N
q
Σiεi e-βεi
εie –βεi = - d
dβ
e-βεi
How to get thermodynamics?
All information about the thermodynamic properties of the system is contained
in the partition function. Thermal wavefunction.
Total energy
Most probable configuration is dominating.
We use Boltzmann distribution.
We know,
1. All E’s are relative
E is the value of U relative to T = 0.
2. Derivative w.r.t. β is partial
as there are other parameters
(such as V) on which energy
depends on.
Partition function gives internal energy of the system.
12. For a process, change in internal energy, U = U(0) + E
U = U(0) + Σi niεi
How to get entropy?
Internal energy changes occur due to change in populations (Ni + dNi)
or energy states (εi + dεi). Consider a general case:
dU = dU(0) + Σi Ni dεi + Σi εi dNi
For constant volume changes, dU = Σi εi dNi
dU = dqrev = TdS dS = dU/T = k β Σiεi dNi
dS = k Σi(∂lnW/∂ Ni ) dNi + kαΣi dNi
Number of molecules do not change. Second term is zero.
dS = k Σi(∂lnW/∂ Ni ) dNi = k (dlnW)
S = klnW
β εi = (∂lnW/∂Ni ) + α
From the derivation of
Boltzmann distribution
α and β are constants
This can be rewritten (after some manipulations) to
S(T) = [U(T) - U(0)]/T + Nk ln q