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`Atoms in Molecules': A Simple Approach

E Theal Stewart

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The principles underlying Moffitt's method of atoms in molecules and Hurley's intra-atomic correlation correction are examined with the minimum of mathematical analysis, initially by reference to a wave function not involving configuration interaction (the simplest wave function for the lowest 1Σ+u state of the hydrogen molecule). Because of variational difficulties in more complex systems, and difficulties of interpretation in all systems, it is suggested that the evidence which Hurley has presented in support of asymptotic energy adjustments, convincing though it seems, should not be taken to justify the use of the intra-atomic correlation correction as a means of improving molecular wave functions.


PACS

31.15.vj Electron correlation calculations for atoms and ions: excited states

31.15.xt Variational techniques

Subjects

Atomic and molecular physics

Computational physics

Dates

Issue 3 (1 March 1960)

Received 9 September 1959



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