| BDE261: A Comprehensive Set of High-Level Theoretical Bond Dissociation Enthalpies. | |
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MedLine Citation:
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PMID: 22587308 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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We have used the high-level W1w protocol to compile a comprehensive collection of 261 bond dissociation enthalpies (BDEs) for bonds connecting hydrogen, first-row and second-row p-block elements. Together they cover 45 bond types, and we term this the BDE261 set. We have used these benchmark values to assess the performance of computationally less demanding theoretical procedures, including density functional theory (DFT), double-hybrid DFT (DHDFT), and high-level composite procedures. We find that the M06-2X (DFT), ROB2-PLYP and DuT-D3 (DHDFT), and G3X(MP2)-RAD and G4(MP2)-6X (composite) procedures yield absolute BDEs with satisfactory to excellent accuracy. Overall, we recommend G4(MP2)-6X as an accurate and relatively cost-effective procedure for the direct computation of BDEs. One important finding is that the deviations for DFT and (especially) DHDFT procedures are often quite systematic. This allows an alternative approach to obtaining accurate absolute BDEs, namely, to evaluate accurate relative BDEs (RBDEs) using a computationally less demanding procedure, and to use these RBDEs in combination with appropriate and accurate reference BDEs to give accurate absolute BDEs. We recommend DuT-D3 for this purpose. For a still less computationally demanding approach, we introduce the deviation from additivity of the RBDE (DARBDE), and demonstrate that the combination of lower-level DARBDEs for larger systems and higher-level (W1w) reference RBDEs and BDEs for small systems can be utilized to obtain improved RBDEs for multiply substituted systems at low cost. |
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Authors:
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Bun Chan; Leo Radom |
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Publication Detail:
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Type: JOURNAL ARTICLE Date: 2012-5-15 |
Journal Detail:
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Title: The journal of physical chemistry. A Volume: - ISSN: 1520-5215 ISO Abbreviation: - Publication Date: 2012 May |
Date Detail:
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Created Date: 2012-5-16 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 9890903 Medline TA: J Phys Chem A Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
Affiliation:
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School of Chemistry and ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, University of Sydney , Sydney, NSW 2006, Australia. |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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