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Quantum functional sensitivity analysis for the 3‐D ( J = 0) H + H 2 reaction
Author(s) -
Chang Johnny,
Brown Nancy J.
Publication year - 1993
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560480852
Subject(s) - saddle point , potential energy , sensitivity (control systems) , bent molecular geometry , total angular momentum quantum number , chemistry , reaction dynamics , saddle , atomic physics , angular momentum , physics , configuration space , quantum , quantum mechanics , geometry , molecule , electronic engineering , engineering , mathematical optimization , organic chemistry , mathematics
The sensitivity of state‐to‐state transition probabilities for the 3‐dimensional H + H 2 hydrogen‐exchange reaction (at zero total angular momentum) has been investigated with respect to variations in the interaction potential. Several regions of configuration space where the dynamics is highly sensitive to inaccuracies in the potential have been identified. These regions of importance vary with collision energy, but do not change as dramatically as the previously studied [J. Chem. Phys. 97 , 6226 (1992)] collinear case. Near the reaction threshold, the dynamics is most sensitive to the saddle point region as expected. At higher energies (about 1.0 to 1.5 eV), however, the inner corner of the potential, where the dynamics “cuts the corner” in going from reactant to product arrangements, is most important for collinear geometries, and the outer corner, where the H 3 conformation is more compact than the transition state conformation, is most important for bent geometries. Surprisingly, the region of the potential traversed by the minimum energy path across the saddle point region has rather insignificant sensitivities at these higher energies. © 1993 John Wiley & Sons, Inc.