| A RASSCF study of free base, magnesium and zinc porphyrins: accuracy versus efficiency. | |
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MedLine Citation:
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PMID: 23296122 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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The restricted-active-space self-consistent-field methodology is successfully applied to the study of free base- and regular metalloporphyrins, the latter containing magnesium and zinc central ions. It is shown that inclusion of all excitations involving the Gouterman frontier orbitals in the RAS2 subspace results in a numerically stable approach, producing highly accurate results at a fraction of the computational cost of the complete-active-space self-consistent-field method, whereas increasing RAS2 beyond this size leads to only modest improvement. Topological and orbital analysis shows that the approach is also able to give a highly accurate description of the electronic wavefunction. Inclusion of the entire π-conjugated subsystem in the active space results in more accurate excitation energies and a reduction in the dependence on the exact form of the perturbational Hamiltonian used to include dynamic correlation. The larger active space also resolves a quantitative disagreement in results obtained with and without the inclusion of dynamic correlation. |
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Authors:
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Andrew Kerridge |
Publication Detail:
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Type: JOURNAL ARTICLE Date: 2013-1-8 |
Journal Detail:
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Title: Physical chemistry chemical physics : PCCP Volume: - ISSN: 1463-9084 ISO Abbreviation: Phys Chem Chem Phys Publication Date: 2013 Jan |
Date Detail:
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Created Date: 2013-1-8 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 100888160 Medline TA: Phys Chem Chem Phys Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
Affiliation:
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Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK. a.kerridge@ucl.ac.uk. |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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