Partition function thermodynamic properties from

We now have equations for the partition functions for the ideal gas and equations for relating the partition functions to the thermodynamic properties. We are ready to derive the equations for calculating the thermodynamic properties from the molecular parameters. As an example, let us calculate Um - t/o.m for the translational motion of the ideal gas. We start with... 

The theory developed for perfect gases could be extended to solids, if the partition functions of crystals could be expressed in terms of a set of vibrational frequencies that correspond to its various fundamental modes of vibration (O Neil 1986). By estimating thermodynamic properties from elastic, structural, and spectroscopic data, Kieffer (1982) and subsequently Clayton and Kieffer (1991) calculated oxygen isotope partition function ratios and from these calculations derived a set of fractionation factors for silicate minerals. The calculations have no inherent temperature limitations and can be applied to any phase for which adequate spectroscopic and mechanical data are available. They are, however, limited in accuracy as a consequence of the approximations needed to carry out the calculations and the limited accuracy of the spectroscopic data. 

Previous work on the thermodynamic properties of clusters used a number of schemes to evaluate the partition function required in Eq. (3.14). In the normal-mode method, " described in the Introduction, the partition function is constructed from the standard partitioning of a polyatomic gas into classical translational and rotational terms and quantum vibrational contributions. In Monte Carlo studies it is usual to employ a state integration technique.In the state integration method Eq. (3.5) is integrated with respect to temperature to obtain... 

In statistical thermodynamics, it is established that we can compute from the partition function several properties. In tables of textbooks, the entropy of gases... 

Now that we have established the complete form of our partition function, how can we determine thermodynamic properties from it We will start with energy. The total energy of the ensemble is given by equation 17.10 ... 

The thermodynamic properties that we have considered so far, such as the internal energy, the pressure and the heat capacity are collectively known as the mechanical properties and can be routinely obtained from a Monte Carlo or molecular dynamics simulation. Other thermodynamic properties are difficult to determine accurately without resorting to special techniques. These are the so-called entropic or thermal properties the free energy, the chemical potential and the entropy itself. The difference between the mechanical emd thermal properties is that the mechanical properties are related to the derivative of the partition function whereas the thermal properties are directly related to the partition function itself. To illustrate the difference between these two classes of properties, let us consider the internal energy, U, and the Fielmholtz free energy, A. These are related to the partition function by ... 

IS thermodynamic properties can be calculated from the partition function. Here we j state some of the most common ... 

There are numerous possible applications for air curtains. For example, air curtains may be used to heat a body of linear dimensions (as used to move the fresh snow from the railway exchanges in Canada) to function as a partition between two parts of one volume to function as a partition between an internal room and an external environment, that have different thermodynamic properties and to shield an opening in a small working volume (see Section 10.4.6). 

Again, therefore, all thermodynamic properties of a system in quantum statistics can be derived from a knowledge of the partition function, and since this is the trace of an operator, we can choose any convenient representation in which to compute it. The most fruitful application of this method is probably to the theory of imperfect gases, and is well covered in the standard reference works.23... 

Table 10.4 lists the rate parameters for the elementary steps of the CO + NO reaction in the limit of zero coverage. Parameters such as those listed in Tab. 10.4 form the highly desirable input for modeling overall reaction mechanisms. In addition, elementary rate parameters can be compared to calculations on the basis of the theories outlined in Chapters 3 and 6. In this way the kinetic parameters of elementary reaction steps provide, through spectroscopy and computational chemistry, a link between the intramolecular properties of adsorbed reactants and their reactivity Statistical thermodynamics furnishes the theoretical framework to describe how equilibrium constants and reaction rate constants depend on the partition functions of vibration and rotation. Thus, spectroscopy studies of adsorbed reactants and intermediates provide the input for computing equilibrium constants, while calculations on the transition states of reaction pathways, starting from structurally, electronically and vibrationally well-characterized ground states, enable the prediction of kinetic parameters. 

Computing thermodynamic properties is the most important validation of simulations of solutions and biophysical materials. The potential distribution theorem (PDT) presents a partition function to be evaluated for the excess chemical potential of a molecular component which is part of a general thermodynamic system. The excess chemical potential of a component a is that part of the chemical potential of Gibbs which would vanish if the intermolecular interactions were to vanish. Therefore, it is just the part of that chemical potential that is interesting for consideration of a complex solution from a molecular basis. Since the excess chemical potential is measurable, it also serves the purpose of validating molecular simulations. 

All thermodynamic properties can be derived from the partition function. It can be shown that the Helmholtz energy, A, is related to Zby the simple expression... 

The partition function provides the bridge to calculating thermodynamic quantities of interest. Using the molecular partition function and formulas derived in this section, we will be able to calculate the internal energy E, the heat capacity Cp, and the entropy S of a gas from fundamental properties of the molecule, such as its mass, moments of inertia, and vibrational frequencies. Thus, if thermodynamic data are lacking for a species of interest, we usually know, or can estimate, these molecular constants, and we can calculate reasonably accurate thermodynamic quantities. In Section 8.6 we illustrate the practical application of the formulas derived here with a numerical example of the thermodynamic properties for the species CH3. 

The grand canonical formalism is useful only provided n[iJ,p] exists in the thermodynamic limit Q — oo. This property is not completely obvious, as becomes dear from an analysis of the canonical partition function Z M Since the positions of all M chains are integrated independently over all the volume, we find... 

With the development of Equation 5.12 relating the partition function and the macroscopic properties, all of the macroscopic thermodynamic properties may be derived from Equation 5.7. For example, differentiating In E with respect to the absolute activity (A.) of./, provides the total number of guest molecules J over all the cavities i... 

Consider the equilibrium between reactants A, B,.. . and products M, N,.. . in the gas phase as well as in solution in a given solvent S (Figure 2.2). The equilibrium constant in the gas phase, K%, depends on the properties of the reactants and the products. In very favourable cases it can be estimated from statistical thermodynamics via the relevant partition functions, but for the present purposes it is regarded as given. The problem is to estimate the magnitude of the equilibrium constant in the solution, A , and how it changes to KP-, when solvent Su is substituted for solvent St. 

Statistical mechanics provides a bridge between the properties of atoms and molecules (microscopic view) and the thermodynmamic properties of bulk matter (macroscopic view). For example, the thermodynamic properties of ideal gases can be calculated from the atomic masses and vibrational frequencies, bond distances, and the like, of molecules. This is, in general, not possible for biochemical species in aqueous solution because these systems are very complicated from a molecular point of view. Nevertheless, statistical mechanmics does consider thermodynamic systems from a very broad point of view, that is, from the point of view of partition functions. A partition function contains all the thermodynamic information on a system. There is a different partition function... 

The semigrand partition function F corresponds with a system of enzyme-catalyzed reactions in contact with a reservoir of hydrogen ions at a specified pH. The semigrand partition function can be written for an aqueous solution of a biochemical reactant at specified pH or a system involving many biochemical reations. The other thermodynamic properties of the system can be calculated from F. 

In addition to being a function of T, the partition function is also a function of V, on which the quantum description of matter tells us that the molecular energy levels, , depend. Because, for single-component systems, all intensive state variables can be written as functions of two state variables, we can think of q(T, V) as a state function of the system. The partition function can be used as one of the independent variables to describe a single-component system, and with one other state function, such as T, it will completely define the system. All other properties of the system (in particular, the thermodynamic functions U, H, S, A, and G) can then be obtained from q and one other state function. 

Structural characteristics of adsorbed chains, such as the mean distance of chain ends from the surface and the fraction of segments in each layer, derive from P(i,s). The partition function and thermodynamic properties depend on the eigenvalues of W (Flory, 1969). In the limit n - oo, calculation of thermodynamic functions simplifies because one eigenvalue, denoted by A, dominates the free energy per segment,... 

To relate these thermodynamic quantities to molecular properties and interactions, we need to consider the statistical thermodynamics of ideal gases and ideal solutions. A detailed discussion is beyond the scope of this review. We note for completeness, however, that a full treatment of the free energy of solvation should include the changes in the rotational and vibrational partition functions for the solute as it passes from the gas phase into solution, AGjnt. ... 

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