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Phase continuity in molecular orbitals: enumeration of zeros in the dipole matrix element

J M Peek1, T Kereselidze2, I Noselidze2 and J Kielkopf3

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The eigenfunctions for an electron in the Coulomb field of two nuclei with arbitrary charge are considered in the Born–Oppenheimer approximation. This forced separation of electron and nuclear variables introduces the magnitude of the internuclear separation R as a parameter. An eigenfunction approaches a hydrogenic ion as R approaches zero and the standard phase convention is applied there. The separated-atom phase is deduced and found to depend on the R = 0 eigenparameters. This is contrary to expectations. These results are used to investigate the sign of the dipole matrix element in the two limits of R. The even/odd number of zeros for a transition over 0 ≤ R < is thereby determined. These results are related to existing numerical data and one omission is identified. Predictions are given. The phase arguments predict sequences of transitions that must have similar properties. One such sequence is investigated. A sum rule result shows a deep minimum exists as a function of R. This result is related to an unusual minimum previously predicted for the photoionization of H2+.


PACS

31.15.-p Calculations and mathematical techniques in atomic and molecular physics

33.70.Ca Oscillator and band strengths, lifetimes, transition moments, and Franck-Condon factors

Subjects

Atomic and molecular physics

Computational physics

Dates

Issue 3 (14 February 2007)

Received 15 June 2006, in final form 4 December 2006

Published 24 January 2007



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