Lecture 1: Historical Overview, Statistical Paradigm, Classical Mechanics
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1 Lecture 1: Historical Overview, Statistical Paradigm, Classical Mechanics Chapter I. Basic Principles of Stat Mechanics A.G. Petukhov, PHYS 743 August 23, 2017 Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
2 Historical Overview According to ancient greek philosophers all matter consists of discrete particles that are permanently moving and interacting. Gas of particles is the simplest object to study. Until 20 th century this molecular-kinetic theory had not been directly confirmed in spite of it s success in chemistry Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
3 Historical Overview According to ancient greek philosophers all matter consists of discrete particles that are permanently moving and interacting. Gas of particles is the simplest object to study. Until 20 th century this molecular-kinetic theory had not been directly confirmed in spite of it s success in chemistry In Einstein and Smoluchovski developed theory of Brownian motion. The theory was experimentally verified in 1908 by a french physical chemist Jean Perrin who was able to estimate the Avogadro number N A with very high accuracy. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
4 Historical Overview According to ancient greek philosophers all matter consists of discrete particles that are permanently moving and interacting. Gas of particles is the simplest object to study. Until 20 th century this molecular-kinetic theory had not been directly confirmed in spite of it s success in chemistry In Einstein and Smoluchovski developed theory of Brownian motion. The theory was experimentally verified in 1908 by a french physical chemist Jean Perrin who was able to estimate the Avogadro number N A with very high accuracy. Daniel Bernoulli in eighteen century was the first who applied molecular-kinetic hypothesis to calculate the pressure of an ideal gas and deduct the empirical Boyle s law pv = const. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
5 Historical Overview According to ancient greek philosophers all matter consists of discrete particles that are permanently moving and interacting. Gas of particles is the simplest object to study. Until 20 th century this molecular-kinetic theory had not been directly confirmed in spite of it s success in chemistry In Einstein and Smoluchovski developed theory of Brownian motion. The theory was experimentally verified in 1908 by a french physical chemist Jean Perrin who was able to estimate the Avogadro number N A with very high accuracy. Daniel Bernoulli in eighteen century was the first who applied molecular-kinetic hypothesis to calculate the pressure of an ideal gas and deduct the empirical Boyle s law pv = const. In the 19th century Clausius introduced the concept of the mean free path of molecules in gases. He also stated that heat is the kinetic energy of molecules. In 1859 Maxwell applied molecular hypothesis to calculate the distribution of gas molecules over their velocities. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
6 Historical Overview, cont d In Ludwig Boltzmann generalized Maxwell s distribution to the case of a gas in an external field and proved the famous equipartition theorem. He also derived his celebrated kinetic equation. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
7 Historical Overview, cont d In Ludwig Boltzmann generalized Maxwell s distribution to the case of a gas in an external field and proved the famous equipartition theorem. He also derived his celebrated kinetic equation. In the first half of the 19 th century the phenomenological thermodynamics was developed. The equivalence of heat and work (the 1 st law of thermodynamics) was stated by Mayer, Joule and Helmholtz. Then Carnot, Clausius and Kelvin formulated the 2 nd law of thermodynamics (the entropy of and isolated system never decreases). Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
8 Historical Overview, cont d In Ludwig Boltzmann generalized Maxwell s distribution to the case of a gas in an external field and proved the famous equipartition theorem. He also derived his celebrated kinetic equation. In the first half of the 19 th century the phenomenological thermodynamics was developed. The equivalence of heat and work (the 1 st law of thermodynamics) was stated by Mayer, Joule and Helmholtz. Then Carnot, Clausius and Kelvin formulated the 2 nd law of thermodynamics (the entropy of and isolated system never decreases). The statistical mechanics in its modern form was formulated as a complete theory by an American physicist Josiah Willard Gibbs in The Gibbs formulation is the summit of the statistical physics. It provides rational justification of thermodynamics and requires only a minor modification to describe quantum statistics. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
9 Historical Overview, cont d In order to understand the magnitude of Gibbs contribution we quote Robert Millikan who said that...[gibbs] did for statistical mechanics and for thermodynamics what Laplace did for celestial mechanics and Maxwell did for electrodynamics, namely, made his field a well-nigh finished theoretical structure. hapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
10 Historical Overview, cont d In order to understand the magnitude of Gibbs contribution we quote Robert Millikan who said that...[gibbs] did for statistical mechanics and for thermodynamics what Laplace did for celestial mechanics and Maxwell did for electrodynamics, namely, made his field a well-nigh finished theoretical structure. In 1900 Max Planck formulated and presented his theory of blacks-body radiation based on a revolutionary quantum hypothesis. This theory started a new era of quantum physics in general and, in particular, the era of quantum statistical mechanics. hapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
11 Statistical Paradigm Statistical physics (mechanics) deals with the special laws that govern behavior and properties of macroscopic bodies, i.e. the bodies containing very large, 10 23, number of particles (atoms or molecules). Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
12 Statistical Paradigm Statistical physics (mechanics) deals with the special laws that govern behavior and properties of macroscopic bodies, i.e. the bodies containing very large, 10 23, number of particles (atoms or molecules). Any attempt to describe macroscopic systems using just equation of motions (classical or quantum) will fail. It is impossible even to write down the equation of motion for a system with s degrees of freedom. Let alone, to solve and analyze these equations. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
13 Statistical Paradigm Statistical physics (mechanics) deals with the special laws that govern behavior and properties of macroscopic bodies, i.e. the bodies containing very large, 10 23, number of particles (atoms or molecules). Any attempt to describe macroscopic systems using just equation of motions (classical or quantum) will fail. It is impossible even to write down the equation of motion for a system with s degrees of freedom. Let alone, to solve and analyze these equations. In spite of this seemingly insurmountable obstacles the macroscopic systems are tractable (the goal of this course is to prove it). Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
14 Statistical Paradigm Statistical physics (mechanics) deals with the special laws that govern behavior and properties of macroscopic bodies, i.e. the bodies containing very large, 10 23, number of particles (atoms or molecules). Any attempt to describe macroscopic systems using just equation of motions (classical or quantum) will fail. It is impossible even to write down the equation of motion for a system with s degrees of freedom. Let alone, to solve and analyze these equations. In spite of this seemingly insurmountable obstacles the macroscopic systems are tractable (the goal of this course is to prove it). We need a new paradigm, recognizing that statistical laws resulting from the very presence of the huge number of particles cannot be in any way reduced to purely mechanical laws. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
15 Statistical Paradigm The systems of many ( ) degrees of freedom are described by the laws of different kind. These laws become invalid for small systems. For instance, the equation of state of an ideal gas: Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
16 Statistical Paradigm The systems of many ( ) degrees of freedom are described by the laws of different kind. These laws become invalid for small systems. For instance, the equation of state of an ideal gas: pv = RT Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
17 Statistical Paradigm The systems of many ( ) degrees of freedom are described by the laws of different kind. These laws become invalid for small systems. For instance, the equation of state of an ideal gas: pv = RT is quite certain and can be checked experimentally with high accuracy. However this equation relates different type of variables (not mechanical ones!), so-called thermodynamic variables (or integral variables, defined by all particles). Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
18 Statistical Paradigm The systems of many ( ) degrees of freedom are described by the laws of different kind. These laws become invalid for small systems. For instance, the equation of state of an ideal gas: pv = RT is quite certain and can be checked experimentally with high accuracy. However this equation relates different type of variables (not mechanical ones!), so-called thermodynamic variables (or integral variables, defined by all particles). The goal of the statistical mechanics is to define these variables and to justify the laws of thermodynamics Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
19 Description of Motion in Classical mechanics We will start with the classical statistics, i.e. consider a mechanical system with s degrees of freedom subject to the Newton s law. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
20 Description of Motion in Classical mechanics We will start with the classical statistics, i.e. consider a mechanical system with s degrees of freedom subject to the Newton s law. The positions of particles in the system will be described by s coordinates q 1, q 2,..., q s Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
21 Description of Motion in Classical mechanics We will start with the classical statistics, i.e. consider a mechanical system with s degrees of freedom subject to the Newton s law. The positions of particles in the system will be described by s coordinates q 1, q 2,..., q s The state of the system at a given instant will be defined by these coordinates and by s velocities: q 1, q 2,..., q s, Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
22 Description of Motion in Classical mechanics We will start with the classical statistics, i.e. consider a mechanical system with s degrees of freedom subject to the Newton s law. The positions of particles in the system will be described by s coordinates q 1, q 2,..., q s The state of the system at a given instant will be defined by these coordinates and by s velocities: q 1, q 2,..., q s, The number s depends on a particular system, e.g. for a system of N particles in 3D space s = 3N. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
23 Description of Motion in Classical mechanics We will start with the classical statistics, i.e. consider a mechanical system with s degrees of freedom subject to the Newton s law. The positions of particles in the system will be described by s coordinates q 1, q 2,..., q s The state of the system at a given instant will be defined by these coordinates and by s velocities: q 1, q 2,..., q s, The number s depends on a particular system, e.g. for a system of N particles in 3D space s = 3N.For any mechanical system a definite function: L = L(q 1, q 2,..., q s, q 1, q 2,..., q s, t) L(q, q, t) called Lagrangian can be introduced. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
24 Least Action Principle The equations of motion can be obtained from the least action principle stating that the integral (action) S = takes the least possible value. q2 (t 2 ) q 1 (t 1 ) L(q, q, t)dt = min Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
25 Least Action Principle The equations of motion can be obtained from the least action principle stating that the integral (action) S = q2 (t 2 ) q 1 (t 1 ) L(q, q, t)dt = min takes the least possible value. Minimization of S yields s equations of motion (Lagrange s equations): ( ) d L L = 0 i = 1,..., s (1) dt q i q i These are s second order differential equations connecting q, q, and q. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
26 Least Action Principle The equations of motion can be obtained from the least action principle stating that the integral (action) S = q2 (t 2 ) q 1 (t 1 ) L(q, q, t)dt = min takes the least possible value. Minimization of S yields s equations of motion (Lagrange s equations): ( ) d L L = 0 i = 1,..., s (1) dt q i q i These are s second order differential equations connecting q, q, and q. For conservative systems L(q, q, t) = T (q, q) U(q), where T = i m ivi 2 /2 is the total kinetic energy and U(q) is the potential energy. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
27 Hamilton s (Canonical) Equations In statistical mechanics another form of equations of motion is used (Hamilton s equations). Introducing generalized momenta: ( ) L p i = q i (2) Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
28 Hamilton s (Canonical) Equations In statistical mechanics another form of equations of motion is used (Hamilton s equations). Introducing generalized momenta: ( ) L p i = q i (2) and Hamiltonian function (using Legendre transformation): H(q, p, t) = s p i q i L(q, q, t) (3) i=1 Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
29 Hamilton s (Canonical) Equations In statistical mechanics another form of equations of motion is used (Hamilton s equations). Introducing generalized momenta: ( ) L p i = q i (2) and Hamiltonian function (using Legendre transformation): H(q, p, t) = s p i q i L(q, q, t) (3) we obtain a set of 2s first-order differential equations (Hamilton s equations): i=1 ṗ i = H q i (4) q i = H p i (5) Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
30 Conservations Laws (Integrals of Motion) A general solution of a system of 2s first order differential equations depends on 2s arbitrary constants. For a conservative, isolated (closed) system the system of equations of motion does not contain the time t (independent variable) explicitly (autonomous system). It means that the equations of motion are time-invariant, i.e. the origin of time t 0 is arbitrary. Since we can always eliminate t 0 there are only 2s 1 combinations of q i and p i that remain constant. These constants are called integrals of motion. There are seven integrals of motion that are of the most significance for statistical mechanics: Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
31 Conservations Laws (Integrals of Motion) A general solution of a system of 2s first order differential equations depends on 2s arbitrary constants. For a conservative, isolated (closed) system the system of equations of motion does not contain the time t (independent variable) explicitly (autonomous system). It means that the equations of motion are time-invariant, i.e. the origin of time t 0 is arbitrary. Since we can always eliminate t 0 there are only 2s 1 combinations of q i and p i that remain constant. These constants are called integrals of motion. There are seven integrals of motion that are of the most significance for statistical mechanics: Energy E resulting from homogeneity of time Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
32 Conservations Laws (Integrals of Motion) A general solution of a system of 2s first order differential equations depends on 2s arbitrary constants. For a conservative, isolated (closed) system the system of equations of motion does not contain the time t (independent variable) explicitly (autonomous system). It means that the equations of motion are time-invariant, i.e. the origin of time t 0 is arbitrary. Since we can always eliminate t 0 there are only 2s 1 combinations of q i and p i that remain constant. These constants are called integrals of motion. There are seven integrals of motion that are of the most significance for statistical mechanics: Energy E resulting from homogeneity of time Three projections of Linear momentum P resulting from homogeneity of space Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
33 Conservations Laws (Integrals of Motion) A general solution of a system of 2s first order differential equations depends on 2s arbitrary constants. For a conservative, isolated (closed) system the system of equations of motion does not contain the time t (independent variable) explicitly (autonomous system). It means that the equations of motion are time-invariant, i.e. the origin of time t 0 is arbitrary. Since we can always eliminate t 0 there are only 2s 1 combinations of q i and p i that remain constant. These constants are called integrals of motion. There are seven integrals of motion that are of the most significance for statistical mechanics: Energy E resulting from homogeneity of time Three projections of Linear momentum P resulting from homogeneity of space Three projections of Angular Momentum M resulting from isotropy of space Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
34 Conservation of Energy Conservation of energy can be proven from time independence of the Hamiltonian at the Hamilton s equations (4). Indeed, for any H(p, q, t): dh dt = H t + s i=1 ( H q i + H ) ṗ i q i p i Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
35 Conservation of Energy Conservation of energy can be proven from time independence of the Hamiltonian at the Hamilton s equations (4). Indeed, for any H(p, q, t): dh dt = H t + s i=1 ( H q i + H ) ṗ i q i p i Using time-independence, i.e. H/ t = 0 and Hamilton s equations (4) we obtain: dh s ( H dt = H H ) H = 0 q i p i p i q i i=1 Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
36 Conservation of Energy Conservation of energy can be proven from time independence of the Hamiltonian at the Hamilton s equations (4). Indeed, for any H(p, q, t): dh dt = H t + s i=1 ( H q i + H ) ṗ i q i p i Using time-independence, i.e. H/ t = 0 and Hamilton s equations (4) we obtain: dh s ( H dt = H H ) H = 0 q i p i p i q i Thus i=1 H(p, q) = E where E is the constant of motion identified as the energy of the system. Chapter I. Basic Principles of Stat MechanicsLecture A.G. Petukhov, 1: Historical PHYS Overview, 743 Statistical Paradigm, Classical August Mechanics 23, / 11
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