Theorem of average

The Theorem of Averages.—We are now in a position to discuss the fundamental theorem of averages10 mentioned earlier. This theorem states that all time averages of the form... 

A specialized notation and terminology is commonly used in discussions involving averages. The right-hand side of the theorem of averages (3-33) is often abbreviated by writing... 

Random Variables.—An interesting and useful interpretation of the theorem of averages is to regard it as a means for calculating the distribution functions of certain time functions Y(t) that are related to a time function X(t) whose distribution function is known. More precisely, if Y(t) is of the form Y(t) = [X(t)], then the theorem of averages enables us to calculate the distribution function of Y(t)... 

The notion of the distribution function of a random variable is also useful in connection with problems where it is not possible or convenient to subject the underlying function X(t) to direct measurements, but where certain derived time functions of the form Y(t) = [X(t)] are available for observation. The theorem of averages then tdls us what averages of X(t) it is possible to calculate when all that is known is the distribution function of . The answer is quite simple if / denotes (almost) apy real-valuqd function of a real variable, then all X averages of the form... 

All averages of the form (3-96) can be calculated in terms of a canonical set of averages called joint distribution functions by means of an extension of the theorem of averages proved in Section 3.3. To this end, we shall define the a order distribution function of X for time spacings rx < r2 < < by the equation,... 

The Multidimensional Theorem of Averages and Some of its Applications.—The multidimensional theorem of averages is a straightforward generalization of equation (3-33), and states that for any function of n + m-real variables... 

The multidimensional theorem of averages can be used to calculate the higher-order joint distribution functions of derived sets of time functions, each of which is of the form... 

Once again, it should be emphasized that the functional form of a set of random variables is important only insofar as it enables us to calculate their joint distribution function in terms of other known distribution functions. Once the joint distribution function of a group of random variables is known, no further reference to their fractional form is necessary in order to use the theorem of averages for the calculation of any time average of interest in connection with the given random variables. 

Each hamionic temi in the Hamiltonian contributes k T to the average energy of the system, which is the theorem of the equipartition of energy. Since this is also tire internal energy U of the system, one can compute the heat capacity... 

Is the temperature 1/0 related to the variance of the momentum distribution as in the classical equipartition theorem It happens that there is no simple generalization of the equipartition theorem of classical statistical mechanics. For the 2N dimensional phase space F = (xi. .. XN,pi,.. -Pn) the ensemble average for a harmonic system is... 

It is difficult to point to the basic reason why the average-potential model is not better applicable to metallic solutions. Shimoji60 believes that a Lennard-Jones 6-12 potential is not adequate for metals and that a Morse potential would give better results when incorporated in the same kind of model. On the other hand, it is possible that the main trouble is that metal solutions do not obey a theorem of corresponding states. More specifically, the interaction eAB(r) may not be expressible by the same function as for the pure components because the solute is so strongly modified by the solvent. This point of view is supported by considerations of the electronic models of metal solutions.46 The idea that the solvent strongly modifies the solute metal is reached also through a consideration of the quasi-chemical theory applied to dilute solutions. This is the topic that we consider next. 

Of course, both statements can be proved from the theorem of uniqueness for the attraction field. In addition, it is appropriate to comment a linear function reaches its maximum at terminal points of the interval. The same behavior is observed in the case of harmonic functions, which cannot have their extreme inside the volume. Otherwise, the average value of the function at some point will not be equal to its value at this point, and, correspondingly, the Laplacian would differ from zero. At the same time, saddle points may exist. 

Eq. (14), which was originally postulated by Zimmerman and Brittin (1957), assumes fast exchange between all hydration states (i) and neglects the complexities of cross-relaxation and proton exchange. Equation (15) is consistent with the Ergodic theorem of statistical thermodynamics, which states that at equilibrium, a time-averaged property of an individual water molecule, as it diffuses between different states in a system, is equal to a... 

Concerning point (b), a generalized theory was developed independently by Prigogine and his co-workers10 11 and by Scott.18 The main idea was to combine the concept of average potential involved in the cell model with the theorem of corresponding states for pure compounds, in such a way that ... 

The estimated uncertainties in the average values bb/ aa and bbAaa °f Tables V and VI are respectively 0-02 and 0.01 (resulting from both experimental errors and deviations from the theorem of corresponding states). This unavoidably leads to rather high inaccuracies in 8 and p (20% in the case of CH4-Kr considered above). 

According to the energy equipartition theorem of classical physics, the three translational kinetic energy modes each acquire average thermal energy kT (where k = R/NA is Boltzmann s constant),... 

A fundamental theorem of classical mechanics called the equipartition theorem (which we shall not derive here) states that the average energy of each degree of freedom of a molecule in a sample at a temperature T is equal to kT. In this simple expression, k is the Boltzmann constant, a fundamental constant with the value 1.380 66 X 10-21 J-K l. The Boltzmann constant is related to the gas constant by R = NAk, where NA is the Avogadro constant. The equipartition theorem is a result from classical mechanics, so we can use it for translational and rotational motion of molecules at room temperature and above, where quantization is unimportant, but we cannot use it safely for vibrational motion, except at high temperatures. The following remarks therefore apply only to translational and rotational motion. 

Equations (5.116), (5.117), and (5.119) characterize the volume-averaging theorems of derivatives [Slattery, 1967b Whitaker, 1969],... 

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