Numerical integration computer methods

There are a number of other methods which may be used to obtain approximate wave functions and energy levels. Five of these, a generalized perturbation method, the Wentzel-Kramers-Brillouin method, the method of numerical integration, the method of difference equations, and an approximate second-order perturbation treatment, are discussed in the following sections. Another method which has been of some importance is based on the polynomial method used in Section 11a to solve the harmonic oscillator equation. Only under special circumstances does the substitution of a series for 4 lead to a two-term recursion formula for the coefficients, but a technique has been developed which permits the computation of approximate energy levels for low-lying states even when a three-term recursion formula is obtained. We shall discuss this method briefly in Section 42c. 

In contrast to the first-order mechanisms just considered, the integrated rate laws for most multistep second (or higher)-order elementary processes can only be determined numerically, using computer methods. However, in many cases of interest the ideas of preequilibrium and steady state are applicable and the kinetic analysis is much simplified. 

By introducing the importance sampling density function concept to adaptive numerical integration, the method provides with moderate computational efforts - for dimensions as high as 15 - accurate estimates... 

Verlet, L. Computer Experiments" on Classical Fluids. I. Thermodynamical Properties of Lennard-Jones Molecules. Physical Review 159 (1967) 98-103 Janezic, D., Merzel, F. Split Integration Symplectic Method for Molecular Dynamics Integration. J. Chem. Inf. Comput. Sci. 37 (1997) 1048-1054 McLachlan, R. I. On the Numerical Integration of Ordinary Differential Equations by Symplectic Composition Methods. SIAM J. Sci. Comput. 16 (1995) 151-168... 

In general, DFT calculations proceed in the same way as Hartree-Fock calculations, with the addition of the evaluation of the extra term, This term cannot be evaluated analytically for DFT methods, so it is computed via numerical integration. 

With modern high-speed computers, an easier method is to numerically integrate equation (6.15), written in the form... 

Values of Vm as a function of p are computed from an equation of state, substituted into equation (6.15). and numerically integrated. In principle, this method can be used to calculate o for any well-behaved equation of state. (It is essentially the method used at the beginning of this section to obtain from the m-BWR equation.)... 

The semiempirical methods represent a real alternative for this research. Aside from the limitation to the treatment of only special groups of electrons (e.g. n- or valence electrons), the neglect of numerous integrals above all leads to a drastic reduction of computer time in comparison with ab initio calculations. In an attempt to compensate for the inaccuracies by the neglects, parametrization of the methods is used. Meaning that values of special integrals are estimated or calibrated semiempirically with the help of experimental results. The usefulness of a set of parameters can be estimated by the theoretical reproduction of special properties of reference molecules obtained experimentally. Each of the numerous semiempirical methods has its own set of parameters because there is not an universial set to calculate all properties of molecules with exact precision. The parametrization of a method is always conformed to a special problem. This explains the multiplicity of semiempirical methods. 

Furthermore, the implementation of the Gauss-Newton method also incorporated the use of the pseudo-inverse method to avoid instabilities caused by the ill-conditioning of matrix A as discussed in Chapter 8. In reservoir simulation this may occur for example when a parameter zone is outside the drainage radius of a well and is therefore not observable from the well data. Most importantly, in order to realize substantial savings in computation time, the sequential computation of the sensitivity coefficients discussed in detail in Section 10.3.1 was implemented. Finally, the numerical integration procedure that was used was a fully implicit one to ensure stability and convergence over a wide range of parameter estimates. 

Later, Kuppermann and Belford (1962a, b) initiated computer-based numerical solution of (7.1), giving the space-time variation of the species concentrations from these, the survival probability at a given time may be obtained by numerical integration over space. Since then, this method has been vigorously followed by others. John (1952) has discussed the convergence requirement for the discretized form of (7.1), which must be used in computers this turns out to be AT/(Ap)2normalized forms of r and t. Often, Ar/(Ap)2 = 1/6 is used to ensure better convergence. Of course, any procedure requires a reaction scheme, values of diffusion and rate coefficients, and a statement about initial number of species and their distribution in space (vide infra). 

Much effort has been devoted to producing fast and efficient numerical integration techniques, and there is a very wide variety of methods now available. The efficiency of an integration routine depends on the number of function evaluations, required to achieve a given degree of accuracy. The number of evaluations depends both on the complexity of the computation and on the number of integration step lengths. The number of steps depends on both the na-... 

As discussed in the introduction to this chapter, the solution of ordinary differential equations (ODEs) on a digital computer involves numerical integration. We will present several of the simplest and most popular numerical-integration algorithms. In Sec, 4.4.1 we will discuss explicit methods and in Sec. 4.4.2 we will briefly describe implicit algorithms. The differences between the two types and their advantages and disadvantages will be discussed. 

Both the numerical and the analytical methods discussed in this chapter can be tedious to carry out, especially with large collections of precise data. Fortunately, the modem digital computer is ideally suited to carry out the repetitive arithmetic operations that are involved. Once a program has been written for a particular computation, whether it be numerical integration or the least-squares fitting of experimental data, it is only necessary to provide a new set of data each time the computation is to be calculated. 

A systematic stepwise method for numerical integration of a rate expression [indeed, of any differential equation y = f(x,y) with an initial value y(Xo) = Vo] to determine the time evolution of the rate process. See also Numerical Computer Methods Numerical Integration Stiffness Gear Algorithm... 

NUMERICAL COMPUTER METHODS NUMERICAL INTEGRATION STIFFNESS GEAR ALGORITHM... 

A different approach in the use of orthogonal polynomials as a transformation method for the population balance is discussed in (8 2.) Here the error in Equation 11 is minimized by the Method of Weighted Residuals. This approach releases the restrictions on the growth rate and MSMPR operation, however, at the cost of the introduction of numerical integration of the integrals involved, which makes the method computationally unattractive. The applicability in determining state space models is presently investigated and results will be published elsewere. 

The Molecular Surface (MS) first introduced by Richards (19) was chosen as the 3D space where the MLP will be calculated. MS specifically refers to a molecular envelope accessible by a solvent molecule. Unlike the solvent accessible surface (20), which is defined by the center of a spherical probe as it is rolled over a molecule, the MS (19), or Connolly surface (21) is traced by the inwardfacing surface of the spherical probe (Fig. 2). The MS consists of three types of faces, namely contact, saddle, and concave reentrant, where the spherical probe touches molecule atoms at one, two, or three points, simultaneously. Calculation of molecular properties on the MS and integration of a function over the MS require a numerical representation of the MS as a manifold S(Mk, nk, dsk), where Mk, nk, dsk are, respectively, the coordinates, the normal vector, and the area of a small element of the MS. Among the published computational methods for a triangulated MS (22,23), the method proposed by Connolly (21,24) was used because it provides a numerical presentation of the MS as a collection of dot coordinates and outward normal vectors. In order to build the 3D-logP descriptor independent from the calculation parameters of the MS, the precision of the MS area computation was first estimated as a function of the point density and the probe radius parameters. When varying... 

---