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Techniques for geometry optimization: A comparison of cartesian and natural internal coordinates
Author(s) -
Baker Jon
Publication year - 1993
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.540140910
Subject(s) - cartesian coordinate system , hessian matrix , log polar coordinates , maxima and minima , bipolar coordinates , geometry , orthogonal coordinates , elliptic coordinate system , curvilinear coordinates , generalized coordinates , coordinate system , computer science , analytic geometry , homogeneous coordinates , local coordinates , range (aeronautics) , mathematics , mathematical analysis , engineering , aerospace engineering
A comparison is made between geometry optimization in Cartesian coordinates, using an appropriate initial Hessian, and natural internal coordinates. Results on 33 different molecules covering a wide range of symmetries and structural types demonstrate that both coordinate systems are of comparable efficiency. There is a marked tendency for natural internals to converge to global minima whereas Cartesian optimizations converge to the local minimum closest to the starting geometry. Because they can now be generated automatically from input Cartesians, natural internals are to be preferred over Z ‐matrix coordinates. General optimization strategies using internal coordinates and/or Cartesians are discussed for both unconstrained and constrained optimization. © John Wiley & Sons, Inc.