Statistics average

The interaction with the solvent is of similar importance as the intramolecuiar energy contributions and a correct representation of the solvent is therefore es.sential. If an explicit solvent description is chosen, averaging over many different solvent configurations is necessary in order to obtain converged statistical averages. Advantageous in this respect is describing the solvent as... 

For purposes of exploring fluctuations and determining the convergence of these statistical averages the root mean square (RMSl deviation m x is also computed ... 

It is important to realize that many important processes, such as retention times in a given chromatographic column, are not just a simple aspect of a molecule. These are actually statistical averages of all possible interactions of that molecule and another. These sorts of processes can only be modeled on a molecular level by obtaining many results and then using a statistical distribution of those results. In some cases, group additivities or QSPR methods may be substituted. 

In the chapter on reaction rates, it was pointed out that the perfect description of a reaction would be a statistical average of all possible paths rather than just the minimum energy path. Furthermore, femtosecond spectroscopy experiments show that molecules vibrate in many dilferent directions until an energetically accessible reaction path is found. In order to examine these ideas computationally, the entire potential energy surface (PES) or an approximation to it must be computed. A PES is either a table of data or an analytic function, which gives the energy for any location of the nuclei comprising a chemical system. 

The rotational isomeric state (RIS) model assumes that conformational angles can take only certain values. It can be used to generate trial conformations, for which energies can be computed using molecular mechanics. This assumption is physically reasonable while allowing statistical averages to be computed easily. This model is used to derive simple analytic equations that predict polymer properties based on a few values, such as the preferred angle... 

HyperChem includes a number of time periods associated with a trajectory. These include the basic time step in the integration of Newton s equations plus various multiples of this associated with collecting data, the forming of statistical averages, etc. The fundamental time period is Atj s At, the integration time step stt in the Molecular Dynamics dialog box. 

As of this writing, the only practical approach to solving turbulent flow problems is to use statistically averaged equations governing mean flow quantities. These equations, which are usually referred to as the Reynolds equations of motion, are derived by Reynold s decomposition of the Navier-Stokes equations (18). The randomly changing variables are represented by a time mean and a fluctuating part ... 

In effect, this represents the root of a statistical average of the squares. The divisor quantity (n — 1) will be referred to as the degrees of freedom. 

The statistical average of a variable described by a probability distribution... 

Under the conditions (1.1) the rate constant is determined by the statistically averaged reactive flux from the initial to the final state. 

Equation (2.2) defines the statistically averaged flux of particles with energy E = P /2m -f V Q) and P > 0 across the dividing surface with Q =0. The step function 6 E — Vq) is introduced because the classical passage is possible only at > Vq. In classically forbidden regions, E < Vq, the barrier transparency is exponentially small and given by the well known WKB expression (see, e.g., Landau and Lifshitz [1981])... 

The first type of interaction, associated with the overlap of wavefunctions localized at different centers in the initial and final states, determines the electron-transfer rate constant. The other two are crucial for vibronic relaxation of excited electronic states. The rate constant in the first order of the perturbation theory in the unaccounted interaction is described by the statistically averaged Fermi golden-rule formula... 

Now we take up the calculation of the rate constant for the decay of a metastable state. In principle it can be done by statistically averaging E from (3.32), but there is a more elegant and general way which relates the rate constant with the imaginary part of free energy. Recalling (3.19) we write the rate constant as... 

In conclusion note that for a sufficiently dense energy spectrum the caustic segments have been shown [Benderskii et al. 1992b] to disappear after statistical averaging, which brings one back to the instanton and, for the present model, leads to eqs. (2.80a, b). 

The term proportional to cTy after averaging goes to zero. It is easy to verify that exp( — overlap integral for the th oscillator [cf. eq. (2.87)],... 

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