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Geometry optimization in density functional methods
Author(s) -
Reveles J. Ulises,
Köster Andreas M.
Publication year - 2004
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20034
Subject(s) - hessian matrix , cartesian coordinate system , geometry , energy minimization , grid , analytic geometry , basis (linear algebra) , regular grid , computer science , computational geometry , algorithm , selection (genetic algorithm) , mathematics , mathematical optimization , computational chemistry , artificial intelligence , chemistry
The geometry optimization in delocalized internal coordinates is discussed within the framework of the density functional theory program deMon. A new algorithm for the selection of primitive coordinates according to their contribution to the nonredundant coordinate space is presented. With this new selection algorithm the excessive increase in computational time and the deterioration of the performance of the geometry optimization for floppy molecules and systems with high average coordination numbers is avoided. A new step selection based on the Cartesian geometry change is introduced. It combines the trust radius and line search method. The structure of the new geometry optimizer is described. The influence of the SCF convergence criteria and the grid accuracy on the geometry optimization are discussed. A performance analysis of the new geometry optimizer using different start Hessian matrices, basis sets and grid accuracies is given. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1109–1116, 2004