Integral method, timings

The Hemian-Kluk method has been developed further [153-155], and used in a number of applications [156-159]. Despite the formal accuracy of the approach, it has difficulties, especially if chaotic regions of phase space are present. It also needs many trajectories to converge, and the initial integration is time consuming for large systems. Despite these problems, the frozen Gaussian approximation is the basis of the spawning method that has been applied to... 

In this paper, we discuss semi-implicit/implicit integration methods for highly oscillatory Hamiltonian systems. Such systems arise, for example, in molecular dynamics [1] and in the finite dimensional truncation of Hamiltonian partial differential equations. Classical discretization methods, such as the Verlet method [19], require step-sizes k smaller than the period e of the fast oscillations. Then these methods find pointwise accurate approximate solutions. But the time-step restriction implies an enormous computational burden. Furthermore, in many cases the high-frequency responses are of little or no interest. Consequently, various researchers have considered the use of scini-implicit/implicit methods, e.g. [6, 11, 9, 16, 18, 12, 13, 8, 17, 3]. 

Note that the same results have not been shown for symmetric (time-reversible) integration methods, although symmetric methods seem to perform quite well in practice. For a discussion of symmetric methods in the context of the QCMD model see [16, 17, 13]. 

In Example 13.1 the initial concentration of analyte is determined by measuring the amount of unreacted analyte at a fixed time. Sometimes it is more convenient to measure the concentration of a reagent reacting with the analyte or the concentration of one of the reaction s products. The one-point fixed-time integral method can still be applied if the stoichiometry is known between the analyte and the species being monitored. For example, if the concentration of the product in the reaction... 

The one-point fixed-time integral method has the advantage of simplicity since only a single measurement is needed to determine the analyte s initial concentration. As with any method relying on a single determination, however, a... 

Fixed-time integral methods are advantageous for systems in which the signal is a linear function of concentration. In this case it is not necessary to determine the concentration of the analyte or product at times ti or f2, because the relevant concentration terms can be replaced by the appropriate signal. For example, when a pseudo-first-order reaction is followed spectrophotometrically, when Beer s law... 

An alternative to a fixed-time method is a variable-time method, in which we measure the time required for a reaction to proceed by a fixed amount. In this case the analyte s initial concentration is determined by the elapsed time, Af, with a higher concentration of analyte producing a smaller Af. For this reason variabletime integral methods are appropriate when the relationship between the detector s response and the concentration of analyte is not linear or is unknown. In the one-point variable-time integral method, the time needed to cause a desired change in concentration is measured from the start of the reaction. With the two-point variable-time integral method, the time required to effect a change in concentration is measured. 

One important application of the variable-time integral method is the quantitative analysis of catalysts, which is based on the catalyst s ability to increase the rate of a reaction. As the initial concentration of catalyst is increased, the time needed to reach the desired extent of reaction decreases. For many catalytic systems the relationship between the elapsed time, Af, and the initial concentration of analyte is... 

Sensitivity The sensitivity for a one-point fixed-time integral method of analysis is improved by making measurements under conditions in which the concentration of the monitored species is larger rather than smaller. When the analyte s concentration, or the concentration of any other reactant, is monitored, measurements are best made early in the reaction before its concentration has substantially decreased. On the other hand, when a product is used to monitor the reaction, measurements are more appropriately made at longer times. For a two-point fixed-time integral method, sensitivity is improved by increasing the difference between times t and f2. As discussed earlier, the sensitivity of a rate method improves when using the initial rate. 

Equation 13.14 shows how [A]o is determined for a two-point fixed-time integral method in which the concentration of A for the pseudo-first-order reaction... 

The total number of integrals computed depends greatiy on the level of complexity of the method time cost savings of 2 orders of magnitude can be realk ab initio theory n vs n ). 

This set of ordinaiy differential equations can be solved using any of the standard methods, and the stability of the integration of these equations is governed by the largest eigenvalue of AA. If Euler s method is used for integration, the time step is hmited by... 

Starting with an initial value of and knowing c t), Eq. (8-4) can be solved for c t + At). Once c t + At) is known, the solution process can be repeated to calciilate c t + 2At), and so on. This approach is called the Euler integration method while it is simple, it is not necessarily the best approach to numerically integrating nonlinear differential equations. To achieve accurate solutions with an Eiiler approach, one often needs to take small steps in time. At. A number of more sophisticated approaches are available that allow much larger step sizes to be taken but require additional calculations. One widely used approach is the fourth-order Bunge Kutta method, which involves the following calculations ... 

Replace the holdup derivatives in Eqs. (13-149) to (13-151) by total-stage material-balance equations (e.g., dMj/dt = Vj + i + Ej- — Vj — Lj) and solve the resulting equations one at a time by the predictor step of an explicit integration method for a time increment that is determined by stability and truncation considerations. If the mole fraclions for a particular stage do not sum to 1, normalize them. 

Note, however, that as In 7r 1 —> 0, the value of ai /x2 — oc since x2 —> 0 at the same time. This integration method works well for determining the activity coefficient of species 2 with a Raoult s law standard state, but it poses difficulties when the integration must be extended to very dilute solutions of component 2 in component 1, as must be done when a Henry s law standard state is chosen for component 2. 

Chromatographic peak areas were measured by both manual and mechanical integration methods. Total analysis time was less than one hour per sample. 

As described in Section 7.3.2 when the integral method is employed, the average specific MAb production rate during any time interval of the batch start-up period... 

The third period corresponds to the last five data points where it is obvious that the assumption of a nearly constant qM is not valid as the slope changes essentially from point to point. Such a segment can still be used and the integral method will provide an average qM, however, it would not be representative of the behavior of the culture during this time interval. It would simply be a mathematical average of a time varying quantity. 

The concentration of each chemical species, as a function of time, during cure can be calculated numerically from Equations 3-6 using the Euler-Romberg Integration method if the initial concentrations of blocked isocyanate and hydroxyl functionality are known. It is a self-starting technique and is generally well behaved under a wide variety of conditions. Details of this numerical procedure are given by McCalla (12). 

Each trial curve generated by the Euler-Romberg integration method is similarly normalized by dividing each of its points by a value corresponding to the time at which the experimental curve reached its maximum. 

Integral methods based on integration of the reaction rate expression. In these approaches one analyzes the data by plotting some function of the reactant concentrations versus time. 

When integral methods are used in data analysis, measured concentrations are used in tests of proposed mathematical formulations of the reaction rate function. One guesses a form of the reaction rate expression on the basis of the reaction stoichiometry and assumptions concerning its mechanism. The assumed expression is then integrated to give a relation between the composition of the reaction mixture and time. A number of such relations were developed in... 

Since the integral method described above is based on the premise that some rate function exists that will lead to a value of i/ Cj) that is linear in time, deviations from linearity (or curvature) indicate that further evaluation or interpretation of the rate data is necessary. Many mathematical functions are roughly linear over sufficiently small ranges of variables. In order to provide a challenging test of the linearity of the data, one should perform at least one experimental run in which data are... 

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