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Non-analyticity of self-consistent field approaches: failure of predicting symmetry

L S Cederbaum, F Tarantelli and P Winkler

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It is found that the Fock operator is not necessarily dilatation analytic in symmetry changing situations. This leads to an unreliability of self-consistent fields to predict symmetry (e.g., the correct point group of a molecule). The analysis shows that the non-analyticity is particularly relevant for open-shell systems. Possibilities to circumvent these difficulties are briefly mentioned. The discussion applies also to the complex rotation method.


PACS

31.15.xr Self-consistent-field methods

Subjects

Atomic and molecular physics

Computational physics

Dates

Issue 22 (28 November 1990)



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