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Canonical Assemble

This is a presentation on canonical ensemble.

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9 views14 pages

Canonical Assemble

This is a presentation on canonical ensemble.

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sarfraznabeeha010
Copyright
© © All Rights Reserved
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CANONICAL

ENSEMBLE
COURSE TITLE: STATISTICAL PHYSICS
COURSE CODE: PHYS-461
PRSENTED TO: DR. SHAHBAZ KHAN
PRESENTED BY
• SYYEDAA AIQA (21014110-004)
• KALSOOM ALAM (21014110-006)
• ESHA TOUQIR (21014110-013)
• MADEEHA NASIR (21014110-019)
• MARYAM MUBEEN (21014110-039)
• ISHA SAIF (21014110-063)
• KANWAL (21814110-001)
Canonical Ensemble
Ensemble:
• A large collection of virtual copies of a system, each
representing a possible state under identical macroscopic
conditions.
• Helps study macroscopic properties by analyzing microscopic
states statistically.
Canonical Ensemble
• Definition: Represents systems in thermal equilibrium with a
heat reservoir at constant temperature TTT.
• Fixed Variables
1. Number of particles (N) 2. Volume (V)
3. Temperature (T)
Probability of Microstate
• A microstate is a specific configuration of the system.
• The energy of a microstate 𝐸𝑖.
• The probabaility of the system being in state 𝑖:
𝑒 −𝛽𝐸
𝑃𝑖 =
𝑍
• Z = partition function, ensuring normalization of probabilities.
1
• 𝛽=
𝑘𝐵 𝑇
• 𝑘𝐵= Boltzmann constant.
Cont….
• Partition Function (ZZZ)
• The cornerstone of statistical mechanics in the canonical
ensemble.
• Defined as:
Z=∑𝑒 −𝛽𝐸𝑖
• Summation over all possible microstates 𝑖.
• For a continuous system, Z involves integration over phase space.

𝑍 = 1/ℎ3𝑁 𝑁! 𝑒 −𝛽𝐻(𝑝,𝑞) 𝑑𝑝𝑑𝑞

Where H(p,q) is the Hamiltonian, h is Planks constant and N!


account for indistinguihability of particles.
Canonical Ensemble and
Thermodynamic Variables
Connection to Thermodynamics
• Helmholtz Free Energy (FFF)
• Key potential for systems at constant T:
F= -𝑘𝛽 𝑇𝐼𝑛 𝑍
• Determines equilibrium and available work.
• Internal Energy (U)
• Average energy: U=-𝜕𝐼𝑛𝑍/𝜕𝛽
• Entropy (S)
Measure of disorder:
𝜕𝐹
S=− = 𝑘𝐵 (𝐼𝑛𝑍 + 𝛽𝑈)
𝜕𝑇
Cont…….
Pressure (P)
𝜕𝐹
• Derived from free energy: P=−( ) 𝑇
𝜕𝑉
Microscopic Perspective
• Microstates with lower 𝐸𝑖 have higher probabilities due to
𝑒 −𝛽𝐸𝑖 .
• Higher T → energy distribution spreads → higher entropy.
Significance
• Canonical ensemble is fundamental in connecting statistical
mechanics with thermodynamic observables.
Entropy of a System in the
Canonical Ensemble
Entropy (S) is a measure of disorder or randomness in a system.
• In statistical mechanics, entropy links the microscopic
behavior of particles to macroscopic thermodynamic
properties.
Entropy in the Canonical Ensemble
• A system in the canonical ensemble has a probability
distribution over microstates 𝑖:
𝑒 −𝛽𝐸𝑖
𝑃𝑖 = , 𝛽 = 1/𝑘𝐵 𝑇
𝑍
where Z is the partition function:
Z=∑​𝑒 −𝛽𝐸
Expression for Entropy
From the Boltzmann Definition:
• S=−𝑘𝐵 ∑𝑃𝑖 𝐼𝑛𝑃𝑖
𝑒 −𝛽𝐸𝑖
Substituting 𝑃𝑖 = :
𝑍
𝑆 = 𝑘𝐵 𝐼𝑛𝑍 + 𝑘𝐵 𝛽 < 𝐸 >
• Thermodynamic Relation:
𝜕𝐼𝑛𝑍
Using U=⟨E⟩=− :
𝜕𝛽
𝑆 = 𝑘𝐵 (𝐼𝑛𝑍 + 𝛽𝑈)
Entropy and Thermodynamic
Connections
Relation to Free Energy (F):
𝜕𝐹
𝑆=− , 𝑤ℎ𝑒𝑟𝑒 𝐹 = −𝑘𝐵 𝑇𝐼𝑛𝑍
𝜕𝑇
Change in Entropy (ΔS):
∆𝑆 = ∆𝑄/𝑇
entropy increases when heat Q is absorbed at temperature T.
Physical Interpretation
• At low temperatures, fewer microstates are accessible (𝑃𝑖
concentrated in low-energy states) → lower S.
• At high temperatures, many microstates become accessible
(𝑃𝑖 spread out) → higher S.
• Entropy quantifies the system's uncertainty or degree of
disorder.
Advantages
• Simplicity in Real-World Modeling: Represents systems at
constant temperature, aligning with many experimental
setups (e.g., controlled-temperature systems).
• Direct Connection to Thermodynamics: Allows computation
of macroscopic properties like entropy, free energy, and
specific heat directly from the partition function.
• Applicability to Small Systems: Works for systems exchanging
energy with large reservoirs.
• Foundation for Simulations: Basis for computational
techniques like canonical Monte Carlo simulations.
Disadvantages

• Energy Fluctuations: Energy is not fixed, making it challenging


to apply to systems with strict energy constraints.
• Complexity in Large Systems: Calculating the partition
function for systems with many microstates can be
computationally expensive or infeasible.
• Limited Applicability: Cannot describe systems with non-
thermal equilibrium constraints (e.g., fixed energy or particle
number fluctuations).
• Assumes Reservoir Interaction: Not suitable for isolated
systems that do not interact with a heat bath.
Applications of Canonical
Ensembles
Applications in Physics and Chemistry
• Thermodynamic Calculations
• Canonical ensembles are used to compute internal energy,
entropy, pressure, and specific heat for systems at constant
TTT.
• Examples: Ideal gases, solids, and quantum systems.
• Phase Transitions
• Analyze phenomena such as melting, boiling, and
magnetization by studying energy distributions and entropy
changes.
• Example: Ising model for magnetic systems.
CONT……
• Molecular Simulations
• Monte Carlo and Molecular Dynamics simulations often
operate within the canonical ensemble to model real-world
conditions.
• Chemical Reactions
• Used to calculate equilibrium constants and reaction rates in
systems at constant temperature.
• Statistical Mechanics of Materials
• Investigates thermal properties of solids and the heat capacity
of materials.

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