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Zusammenfassung
A gradient projection algorithm is presented that permits the application of several constraints during geometry optimization on electronic potential energy surfaces (PES) or conical intersection (CI) seams. The algorithm generalizes the idea recently published in this journal for the optimization of conical intersection geometries. Singular value decompn. is used to transform all constraints, ...
Zusammenfassung
A gradient projection algorithm is presented that permits the application of several constraints during geometry optimization on electronic potential energy surfaces (PES) or conical intersection (CI) seams. The algorithm generalizes the idea recently published in this journal for the optimization of conical intersection geometries. Singular value decompn. is used to transform all constraints, including those related to maintaining the CI, to a new set of constraints with orthogonal gradients. The constraints need not be satisfied at the initial geometry but will be upon convergence. A procedure is presented that dets. relaxed energy paths (REP) connecting two ref. structures on a potential energy surface, or the conical intersection space, without the need to assign an internal coordinate as the reaction coordinate. Examples are presented of optimizations of min. energy structures and REPs in the CI space and REPs on a single electronic PES.
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