The nature of electron correlation in a dissociating bond
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Hollett, Joshua W.; McKemmish, Laura K.; Gill, Peter M. W.
Description
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...[Show more]
dc.contributor.author | Hollett, Joshua W. | |
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dc.contributor.author | McKemmish, Laura K. | |
dc.contributor.author | Gill, Peter M. W. | |
dc.date.accessioned | 2015-12-18T00:37:57Z | |
dc.date.available | 2015-12-18T00:37:57Z | |
dc.identifier.issn | 0021-9606 | |
dc.identifier.uri | http://hdl.handle.net/1885/95097 | |
dc.description.abstract | 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. | |
dc.description.sponsorship | J. W. H. thanks the Natural Sciences and Engineering Research Council (NSERC) of Canada for funding. L.K.M. thanks the RSC for a Summer Research Scholarship. P.M.W.G. thanks the NCI National Facility for a generous grant of supercomputer time and the Australian Research Council (Grant Nos. DP0984806 and DP1094170). | |
dc.publisher | American Institute of Physics (AIP) | |
dc.rights | http://www.sherpa.ac.uk/romeo/issn/0021-9606..."Publishers version/PDF may be used on author's personal website, institutional website or institutional repository" from SHERPA/RoMEO site (as at 18/12/15). Copyright 2011 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in The Journal of Chemical Physics and may be found at https://doi.org/10.1063/1.3599937 | |
dc.source | The Journal of Chemical Physics | |
dc.subject | Keywords: Correlation energy; Dissociating bonds; Double photoionization; Electron correlation effect; Full configuration interaction; Homolytic bonds; Restricted Hartree-fock; Spin-orbitals; Unrestricted Hartree-Fock; Young-type interference pattern; Electron corr | |
dc.title | The nature of electron correlation in a dissociating bond | |
dc.type | Journal article | |
local.description.notes | Imported from ARIES | |
local.identifier.citationvolume | 134 | |
dc.date.issued | 2011-06-10 | |
local.identifier.absfor | 030701 | |
local.identifier.ariespublication | u9911292xPUB225 | |
local.publisher.url | https://www.aip.org/ | |
local.type.status | Published Version | |
local.contributor.affiliation | Hollett, Joshua, College of Physical and Mathematical Sciences, CPMS Research School of Chemistry, RSC General, The Australian National University | |
local.contributor.affiliation | McKemmish, Laura, College of Physical and Mathematical Sciences, CPMS Research School of Chemistry, RSC General, The Australian National University | |
local.contributor.affiliation | Gill, Peter, College of Physical and Mathematical Sciences, CPMS Research School of Chemistry, RSC General, The Australian National University | |
dc.relation | http://purl.org/au-research/grants/arc/DP0984806 | |
dc.relation | http://purl.org/au-research/grants/arc/DP1094170 | |
local.identifier.essn | 1089-7690 | |
local.bibliographicCitation.issue | 22 | |
local.bibliographicCitation.startpage | 224103 | |
local.identifier.doi | 10.1063/1.3599937 | |
local.identifier.absseo | 970102 | |
local.identifier.absseo | 970103 | |
dc.date.updated | 2016-02-24T12:14:19Z | |
local.identifier.scopusID | 2-s2.0-79959409810 | |
local.identifier.thomsonID | 000291660200003 | |
Collections | ANU Research Publications |
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