Rigorous Optimization (rigorous + optimization)

Distribution by Scientific Domains


Selected Abstracts


Orbital-orthogonality constraints and basis-set optimization

JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 6 2006
Fabio E. Penotti
Abstract A new procedure is presented for introducing arbitrary orbital-orthogonality constraints in the variational optimization of otherwise nonorthogonal multiconfiguration electronic wave functions. It is based on suitable analytical changes to the expressions for the first and second derivatives of the electronic energy with respect to the independent variational parameters, and can be applied in the presence of symmetry constraints. It is tested using a second-derivative optimization procedure, the Optimized Basis Set,Generalized Multiconfiguration Spin-Coupled (OBS-GMCSC) approach, that can treat basis-function exponential parameters as variational parameters, to be optimized simultaneously with configuration, spin-coupling, and orbital coefficients. This enables rigorous optimization of basis-set exponential parameters even for fully orthogonal multiconfiguration wave functions. Test calculations are carried out, with optimized even-tempered basis sets, on Li2 and on the CH radical. For the latter, special attention is paid to the electronic spin density at the nuclei. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 762,772, 2006 [source]


An algorithm for the use of surrogate models in modular flowsheet optimization

AICHE JOURNAL, Issue 10 2008
José A. Caballero
Abstract In this work a methodology is presented for the rigorous optimization of nonlinear programming problems in which the objective function and (or) some constraints are represented by noisy implicit black box functions. The special application considered is the optimization of modular process simulators in which the derivatives are not available and some unit operations introduce noise preventing the calculation of accurate derivatives. The black box modules are substituted by metamodels based on a kriging interpolation that assumes that the errors are not independent but a function of the independent variables. A Kriging metamodel uses non-Euclidean measure of distance to avoid sensitivity to the units of measure. It includes adjustable parameters that weigh the importance of each variable for obtaining a good model representation, and it allows calculating errors that can be used to establish stopping criteria and provide a solid base to deal with "possible infeasibility" due to inaccuracies in the metamodel representation of objective function and constraints. The algorithm continues with a refining stage and successive bound contraction in the domain of independent variables with or without kriging recalibration until an acceptable accuracy in the metamodel is obtained. The procedure is illustrated with several examples. © 2008 American Institute of Chemical Engineers AIChE J, 2008 [source]


Shortcut method for kinetically controlled reactive distillation systems

AICHE JOURNAL, Issue 6 2003
J. W. Lee
A geometric-based shortcut method for reactive distillation is addressed. The rectification body method for nonreactive distillation, the concept of critical Damköhler numbers, and the geometric design method for reactive distillation are combined with a new eigenvector analysis of pinch points. This shortcut method provides a minimum or reasonable Damköhler number for a given heat duty, as well as the design implication of how to effectively distribute reaction zones inside a column. This method can be used for a fast screening of process design alternatives and for an initialization of rigorous optimization. [source]


Copper-Catalyzed Asymmetric Conjugate Addition of Trialkylaluminium Reagents to Trisubstituted Enones: Construction of Chiral Quaternary Centers

CHEMISTRY - A EUROPEAN JOURNAL, Issue 34 2007
Magali Vuagnoux-d'Augustin
Abstract Me3Al, Et3Al, and vinylalane species undergo enantioselective conjugate addition to a wide range of 2- or 3-substituted enones (cyclopent-2-enones, cyclohex-2-enones, 3-methyl cyclohept-2-enone) in the presence of catalytic amount of copper salt (copper thiophene carboxylate, [Cu(CH3CN)4]BF4 or [CuOTf]2,C6H6) and tropos-phosphoramidite-based ligand. Thus, chiral quaternary centers can be built, with up to 98,% ee after rigorous optimization of experimental conditions. It was shown that the main important parameter was the order of the introduction of the reagents. Then, the generated enantioenriched aluminium enolates and the chiral conjugate adducts were functionalized and used for subsequent reactions. [source]