ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Two aspects of the problems of calculating steepest descent paths and locating stationary points on surfaces E(X), which are sources of some confusion in the literature, are addressed. These include writing proper expressions for the gradient and Hessian, and their transformation properties relative to coordinate transformations, based on the invariance of the surface E(X). The appropriate transformation is derived, based on a constrained energy minimization condition, to achieve what we call the Hessian eigenvalue representation. This not only allows decoupling of the variables, but also points to the minimization direction and preserves the eigenvalues of the Hessian. These results allow one to use the steepest descent path and stationary point location algorithms in any coordinate system and obtain invariant results. The validity of these considerations are also confirmed through numerical examples. The stationary condition with constrained kinematic path length is also shown to yield a Hessian eigenvalue representation for the normal modes for small vibrations. Lastly, we have constructed a mathematically consistent definition of mass-weighted Cartesians where the intrinsic reaction path of Fukui is a steepest descent path. © 1992 John Wiley & Sons, Inc.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560430610
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