Constrained methods positivity

Perhaps the benefits of physical-realizability constraints, particularly ordinate bounds such as positivity, have not been sufficiently recognized. Surely everyone agrees in principle that such constraints are desirable. Even the early literature on this subject frequently mentions their potential advantages. For one reason or another, however, the earliest nonlinear constrained methods did not fully reveal the inherent power of constraints. 

For the present work, we chose the constrained method described by Jansson (1968) and Jansson et al (1968, 1970). See also Section V.A of Chapter 4 and supporting material in Chapter III. This method has also been applied to ESCA spectra by McLachlan et al (1974). In our adaptation (Jansson and Davies, 1974) the procedure was identical to that used in the original application to infrared spectra except that the data were presmoothed three times instead of once, and the variable relaxation factor was modified to accommodate the lack of an upper bound. Referring to Eqs. (15) and (16) of Section V.A.2 of Chapter 4, we set k = 2o(k)K0 for 6(k) < j and k = Kq exp[3 — for o(k) > This function is seen to apply the positivity constraint in a manner similar to that previously employed but eliminates the upper bound in favor of an exponential falloff. We also experimented with k = k0 for o(k) > j, and found it to be equally effective. As in the infrared application, only 10 iterations were needed. 

The projected symplectic constrained method (4.20)-(4.24) is only first order accurate. We forego providing a detailed proof of this fact, but note that it could be demonstrated using standard methods [164]. Note that (4.20)-(4.24) reduces to the symplectic Euler method in the absence of constraints, and the projection of the momenta would not alter this fact. There are several constraint-preserving, second-order alternatives which generalize the Stormer-Verlet scheme. One of these is the SHAKE method [322]. The original derivation of the SHAKE method began from the position-only, two-step form of the Stormer rule for q = F(q)... 

A similar effect is obtained by using the spin-constrained UHF method (SUHF). In this method, the spin contamination error in a UHF wave function is constrained by the use of a Lagrangian multiplier. This removes the spin contamination completely as the multiplier goes to infinity. In practice, small positive values remove most of the spin contamination. 

Therefore, although the stability function was found to be positive at all the experimental conditions it becomes negative at mole fractions between 0 and the first measured data point. Obviously, if there were additional data available in this region, the simplified constrained LS method that was followed above would have yielded interaction parameters that do not result in prediction of false liquid phase splitting. 

Like penalty methods, barrier methods convert a constrained optimization problem into a series of unconstrained ones. The optimal solutions to these unconstrained subproblems are in the interior of the feasible region, and they converge to the constrained solution as a positive barrier parameter approaches zero. This approach contrasts with the behavior of penalty methods, whose unconstrained subproblem solutions converge from outside the feasible region. 

Although satisfactory criteria for deciding whether data are better analyzed by distributions or multiexponential sums have yet to established, several methods for determining distributions have been developed. For pulse fluorometry, James and Ware(n) have introduced an exponential series method. Here, data are first analyzed as a sum of up to four exponential terms with variable lifetimes and preexponential weights. This analysis serves to establish estimates for the range of the preexponential and lifetime parameters used in the next step. Next, a probe function is developed with fixed lifetime values and equal preexponential factors. An iterative Marquardt(18) least-squares analysis is undertaken with the lifetimes remaining fixed and the preexponential constrained to remain positive. When the preexponential... 

By making the substitution for H and after some algebra taking the limit, he obtained a set of simultaneous nonlinear equations for the Fourier coefficients. Howard solved these equations by an efficient iterative method. His solutions are comparable to the best that we have come to expect from the positive-constrained restoring methods. 

Constraining the solution to be positive can nevertheless provide the added benefits of reduced sensitivity to noise and improved resolution. Gold s iterative ratio method (Chapter 1, Section IV.A), for example, has been used successfully by a number of workers, including MacNeil and Dixon (1977) and Delwicke et al. (1980). MacNeil and Delwicke have compared it with the standard Van Cittert method, which is linear. 

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