Systems of identical particles

The postulates 1 to 6 of quantum meehanies as stated in Sections 3.7 and 7.2 apply to multi-particle systems provided that each of the particles is distinguishable from the others. For example, the nucleus and the electron in a hydrogen-like atom are readily distinguishable by their differing masses and charges. When a system contains two or more identical particles, however, postulates 1 to 6 are not sufficient to predict the properties of the system. These postulates must be augmented by an additional postulate. This chapter introduces this new postulate and discusses its consequences. 

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It is beyond the scope of these introductory notes to treat individual problems in fine detail, but it is interesting to close the discussion by considering certain, geometric phase related, symmetry effects associated with systems of identical particles. The following account summarizes results from Mead and Truhlar [10] for three such particles. We know, for example, that the fermion statistics for H atoms require that the vibrational-rotational states on the ground electronic energy surface of NH3 must be antisymmetric with respect to binary exchange... 

Q is given by Equation (6.4) for a system of identical particles. We shall ignore any normalisation constants in our treatment here to enable us to concentrate on the basics, and so it does not matter whether the system consists of identical or distinguishable particles. We also replace the Hamiltonian by the energy, E. The internal energy is obtained via Equation (6.20) ... 

The completeness relation for a multi-dimensional wave function is given by equation (3.32). However, this expression does not apply to the wave functions vs,A for a system of identical particles because vs,a are either symmetric or antisymmetric, whereas the right-hand side of equation (3.32) is neither. Accordingly, we derive here the appropriate expression for the completeness relation or, as it is often called, the closure property for vs,a-... 

Since the Hamiltonian is symmetric in space coordinates the time-dependent Schrodinger equation prevents a system of identical particles in a symmetric state from passing into an anti-symmetric state. The symmetry character of the eigenfunctions therefore is a property of the particles themselves. Only one eigenfunction corresponds to each eigenfunction and hence there is no exchange degeneracy. 

The Pauli antisymmetry principle tells us that the wave function (including spin degrees of freedom), and thus the basis functions, for a system of identical particles must transform like the totally antisymmetric irreducible representation in the case of fermions, or spin (for odd k) particles, and like the totally symmetric irreducible representation in the case of bosons, or spin k particles (where k may take on only integer values). 

The Eyring analysis does not explicity take chain structures into account, so its molecular picture is not obviously applicable to polymer systems. It also does not appear to predict normal stress differences in shear flow. Consequently, the mechanism of shear-rate dependence and the physical interpretation of the characteristic time t0 are unclear, as are their relationships to molecular structure and to cooperative configurational relaxation as reflected by the linear viscoelastic behavior. At the present time it is uncertain whether the agreement with experiment is simply fortuitous, or whether it signifies some kind of underlying unity in the shear rate dependence of concentrated systems of identical particles, regardless of their structure and the mechanism of interaction. 

Special attention must be paid in systems of identical particles, where we have to take into account the symmetry postulate of quantum mechanics. This means that the space of states for fermions is the antisymmetric subspace of while the symmetric subspace dK+N refers to bosons. 

Statistical mechanics was originally formulated to describe the properties of systems of identical particles such as atoms or small molecules. However, many materials of industrial and commercial importance do not fit neatly into this framework. For example, the particles in a colloidal suspension are never strictly identical to one another, but have a range of radii (and possibly surface charges, shapes, etc.). This dependence of the particle properties on one or more continuous parameters is known as polydispersity. One can regard a polydisperse fluid as a mixture of an infinite number of distinct particle species. If we label each species according to the value of its polydisperse attribute, a, the state of a polydisperse system entails specification of a density distribution p(a), rather than a finite number of density variables. It is usual to identify two distinct types of polydispersity variable and fixed. Variable polydispersity pertains to systems such as ionic micelles or oil-water emulsions, where the degree of polydispersity (as measured by the form of p(a)) can change under the influence of external factors. A more common situation is fixed polydispersity, appropriate for the description of systems such as colloidal dispersions, liquid crystals, and polymers. Here the form of p(cr) is determined by the synthesis of the fluid. 

The aim of this Chapter is the development of an uniform model for predicting diffusion coefficients in gases and condensed phases, including plastic materials. The starting point is a macroscopic system of identical particles (molecules or atoms) in the critical state. At and above the critical temperature, Tc, the system has a single phase which is, by definition, a gas or supercritical fluid. The critical temperature is a measure of the intensity of interactions between the particles of the system and consequently is a function of the mass and structure of a particle. The derivation of equations for self-diffusion coefficients begins with the gaseous state at pressures p below the critical pressure pc. A reference state of a hypothetical gas will be defined, for which the unit value D = 1 m2/s is obtained at p = 1 Pa and a reference temperature, Tr. Only two specific parameters, Tc, and the critical molar volume, VL, of the mono-... 

By definition, the Hamiltonian of a system of identical particles is invariant under the interchange of all the coordinates of any two particles. The wave function describing the system must be either symmetric or antisymmetric under this interchange. If the particles have integer spin, the wavefunction is symmetric and the particles are called bosons if they have half-integer spins, the wavefunction is antisymmetric and the particles are fermions. Our discussion will be restricted to electrons, which are fermions. 

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