ISSN:
0192-8651
Keywords:
Chemistry
;
Theoretical, Physical and Computational Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Computer Science
Notes:
A comparison is made between geometry optimization in Cartesian coordinates, in Z-matrix coordinates, and in natural internal coordinates for the location of transition states. In contrast to the situation with minima, where all three coordinate systems are of comparable efficiency if a reliable estimate of the Hessian matrix is available at the starting geometry, results for 25 different transition states covering a wide range of structural types demonstrate that in practice Z-matrix coordinates are generally superior. For Cartesian coordinates, the commonly used Hessian update schemes are unable to guarantee preservation of the necessary transition state eigenvalue structure, while current algorithms for generating natural internal coordinates may have difficulty handling the distorted geometries associated with transition states. The widely used Eigenvector Following (EF) algorithm is shown to be extremely efficient for optimizing transition states. © 1996 by John Wiley & Sons, Inc.
Additional Material:
5 Tab.
Type of Medium:
Electronic Resource
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