ISSN:
1432-2234
Keywords:
Potential surfaces
;
Conformation analysis
;
Reaction topology
;
Multicenter interactions
;
Symmetry
;
Periodicity
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract Symmetry and periodicity of potential energy surfaces of chemical reactions and conformational changes are determined by the symmetry properties of the nuclear frameworks of all possible nuclear configurations of the given overall stoichiometry. For example, a mirror plane of a nuclear configuration implies a mirror plane of the potential surface (or that of the potential energy hypersurface in higher dimensions), and a local rotational symmetry of substituents implies a translational symmetry, that is, periodicity of the potential surface, if the latter is defined in terms of the usual bond length/bond angle internal coordinates. Such symmetry relations on potential surfaces are rather trivial consequences of molecular symmetry properties; however, when taken collectively for entire domains of nuclear configurations, they lead to nontrivial conclusions. Whereas symmetry properties and energy contents of individual conformations can be studied locally within limited domains of the potential surface, a global analysis of the potential surface may reveal significantly more. In this note, some consequences of the above approach are explored, and a simple test is proposed for the detection and evaluation of the importance of multicenter interactions in conformers related to one another by bond rotations.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00528206
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