The nature of electron correlation in a dissociating bond | Zendy

Joshua W. Hollett | Zendy; L. K. McKemmish | Zendy; Peter M. W. Gill | Zendy

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The nature of electron correlation in a dissociating bond

Author(s) -

Joshua W. Hollett,

L. K. McKemmish,

Peter M. W. Gill

Publication year - 2011

Publication title -

the journal of chemical physics

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.071

H-Index - 357

eISSN - 1089-7690

pISSN - 0021-9606

DOI - 10.1063/1.3599937

Subject(s) - electronic correlation , ultra high frequency , atomic physics , photoionization , electron , momentum (technical analysis) , chemistry , atomic orbital , position and momentum space , physics , molecular physics , ionization , quantum mechanics , ion , telecommunications , finance , computer science , economics

We have constructed the unrestricted Hartree-Fock (UHF), restricted Hartree-Fock (RHF), and full configuration interaction (FCI) position and momentum intracules and holes for H···H at bond lengths R from 1 to 10 bohrs. We trace the recently discovered inversion of the UHF position hole at intermediate R to over-localization of the spin-orbitals, and support this by a correlation energy component analysis. The RHF and UHF momentum holes are found to be more complicated; however their features are explained through decomposition of electron correlation effects. The UHF momentum hole is also found to invert and exhibits interesting behavior at large R. The RHF (but not UHF) and FCI momentum intracules exhibit Young-type interference patterns related to recent double photoionization experiments. Our analyses yield the most comprehensive picture to date of the behavior of the electrons during homolytic bond fission.

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