Statistics quantum

The Gibbs formulation of an equilibrium statistics is in error when applied to the internal motions of molecules and also to the external motions of light molecules such as helium or hydrogen at low temperatures. 

The difficulty arises from the restrictions placed upon the mechanical behavior of such systems by quantum mechanics. Whereas a system that follows the laws of classical mechanics may assume any given mechanical configuration and any given energy, the laws of quantum mechanics restrict the energy of many systems to a discrete number of possible values. 

To take a very simple example, an ideal gas molecule in a cubic box of side I may only take on translational energies given by Et = hr/SmP) nx + Uy- + where h is Planck s constant, m is the mass, and n, are numbers which may take on only integral values 1, 2, 3, 

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The set of microstates of a finite system in quantum statistical mechanics is a finite, discrete denumerable set of quantum states each characterized by an appropriate collection of quantum numbers. In classical statistical mechanics, the set of microstates fonn a continuous (and therefore infinite) set of points in f space (also called phase space). 

The leading correction to the classical ideal gas pressure temi due to quantum statistics is proportional to 1 and to n. The correction at constant density is larger in magnitude at lower temperatures and lighter mass. The coefficient of can be viewed as an effective second virial coefficient The effect of quantum... 

Yamamoto T 1960 Quantum statistical mechanical theory of the rate of exchange chemical reactions in the gas phase J. Chem. Phys. 33 281... 

Only in the high-energy limit does classical statistical mechanics give accurate values for the sum and density of states tenns in equation (A3.12.15) [3,14]. Thus, to detennine an accurate RRKM lc(E) for the general case, quantum statistical mechanics must be used. Since it is difficult to make anliannonic corrections, both the molecule and transition state are often assumed to be a collection of hannonic oscillators for calculating the... 

Louisell W H 1973 Quantum Statistical Properties of Radiation (New York Wiley)... 

Tuckerman M E and Hughes A 1998 Path integral molecular dynamics a computational approach to quantum statistical mechanics Classical and Quantum Dynamics In Condensed Phase Simulations ed B J Berne, G Ciccotti and D F Coker (Singapore World Scientific) pp 311-57... 

Cao, J., Voth, G.A. The formulation of quantum statistical mechanics based on the Feynman path centroid density. I. Equilibrium properties. J. Chem. Phys. 100 (1994) 5093-5105 II Dynamical properties. J. Chem. Phys. 100 (1994) 5106-5117 III. Phase space formalism and nalysis of centroid molecular dynamics. J. Chem. Phys. 101 (1994) 6157-6167 IV. Algorithms for centroid molecular dynamics. J. Chem. Phys. 101 (1994) 6168-6183 V. Quantum instantaneous normal mode theory of liquids. J. Chem. Phys. 101 (1994) 6184 6192. 

Many interesting quantum effects appear at low temperatures due to the effect of quantum statistics. Very interesting PIMC studies of such effects have been done for structural phase transitions in adsorbed " He and He layers [90-91] and for the superfluidity of H2 layers [92]. For studies of related systems and additional information see Sec. IV D 2. 

For the PIMC study of quantum statistics effects in He systems and additional references see Refs. 90, 91. 

Permutations of this type have to be considered in PIMC simulations if a full account of the quantum statistics is intended in the study and required by the physical effect under consideration, which means that additional permutation moves have to be done in the simulation. In this way quantum statistics has been included in a few PIMC simulations, in particular for the study of superfluidity in He [287] and in adsorbed H2 layers [92], for the Bose-Einstein condensation of hard spheres [269], and for the analysis of... 

All these multifarious activities took a lot of Einstein s energies but did not keep him from his physics research. In 1922 he published Ins first paper on unified field theoiy, an attempt at incorporating not only gravitation but also electromagnetism into a new world geometry, a subject that was his main concern until the end of his life. He tried many approaches none of them have worked out. In 1924 he published three papers on quantum statistical mechanics, which include his discoveiy of so-called Bose-Einstein condensation. This was his last contribution to physics that may be called seminal. He did continue to publish all through his later years, however. 

Among the usual advantages of such expressions as Eq. (7-80) and (7-81), one is salient they show forth the invariance of p and w with respect to the choice of the basis functions, u, in terms of which p, a, and P are expressed. The trace, as will be recalled, is invariant against unitary transformations, and the passage from one basis to another is performed by such transformations. The trace is also indifferent to an exchange of the two matrix factors, which is convenient in calculations. Finally, the statistical matrix lends itself to a certain generalization of states from pure cases to mixtures, required in quantum statistics and the theory of measurements we turn to this question in Section 7.9. 

Object.—Quantum statistics was discussed briefly in Chapter 12 of The Mathematics of Physics and Chemistry, and as far as elementary treatments of quantum statistics are concerned,1 that introductory discussion remains adequate. In recent years, however, a spectacular development of quantum field theory has presented us with new mathematical tools of great power, applicable at once to the problems of quantum statistics. This chapter is devoted to an exposition of the mathematical formalism of quantum field theory as it has been adapted to the discussion of quantum statistics. The entire structure is based on the concepts of Hilbert space, and we shall devote a considerable fraction of the chapter to these concepts. 

D. ter Haar, Elements of Statistical Mechanics, Holt, Rinehart, and Winston, New York, 1954 W. Band, Introduction to Quantum Statistics, D. Van Nostrand Co., Inc., Princeton, N.J., 1955. 

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