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The Geometrical Nature of Transition State Variation
Author(s) -
Harris J. Milton,
Paul J. Lawrence
Publication year - 1985
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.198500115
Subject(s) - chemistry , saddle point , diagonal , surface (topology) , movement (music) , saddle , visualization , point (geometry) , geometry , statistical physics , state (computer science) , artificial intelligence , algorithm , physics , mathematical optimization , mathematics , computer science , acoustics
The proposal that the movement of transition states on potential energy surfaces is controlled by the geometry of the surface is examined by use of a nonchemical, mathematical model of surfaces. We conclude that the chemical rules of Thornton, Jencks, and More O'Ferrall for predicting TS movement have an underlying geometrical origin. The model permits ready visualization of the rules for predicting TS movement, and the model facilitates predicting TS movement for surfaces in which the saddle point lies off the diagonals connecting the corners of the surface.