A pseudopotential-based composite method: the relativistic pseudopotential correlation consistent composite approach for molecules containing 4d transition metals (Y-Cd)

The correlation consistent composite approach (ccCA) has proven to be an effective first-principles-based composite approach for main group and first-row transition metal species. By combining relativistic pseudopotentials and ccCA, accurate energetic and thermodynamic data for heavier elements, inc...

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Bibliographic Details
Published in:The Journal of chemical physics 2011-12, Vol.135 (21), p.214103-214103
Main Authors: Laury, Marie L, DeYonker, Nathan J, Jiang, Wanyi, Wilson, Angela K
Format: Article
Language:English
Subjects:
Computer Simulation
Models, Chemical
Quantum Theory
Thermodynamics
Transition Elements - chemistry
Online Access:Get full text
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Summary:The correlation consistent composite approach (ccCA) has proven to be an effective first-principles-based composite approach for main group and first-row transition metal species. By combining relativistic pseudopotentials and ccCA, accurate energetic and thermodynamic data for heavier elements, including transition metals, is obtainable. Relativistic pseudopotential ccCA (rp-ccCA) was formulated and tested on 25 molecules from the G3∕05 set that contain 4p elements (Ga-Kr). A 32.5% time savings was obtained using rp-ccCA, relative to ccCA employing all-electron basis sets. When implementing rp-ccCA to compute dissociation energies and enthalpies of formation for molecules from the 4p block, rp-ccCA results in a mean absolute deviation of 0.89 kcal mol(-1) from experimental data. rp-ccCA was also applied to a set of 30 4d transition metal-containing molecules, ranging from diatomics to Mo(CO)(6), and enthalpies of formation for these species were obtained with a mean absolute deviation of 2.89 kcal mol(-1) in comparison to experimental data. Based on quality of the experimentally available enthalpies of formation, where the average value of reported experimental error bars is 3.43 kcal mol(-1), rp-ccCA is within transition metal chemical accuracy for the 4d molecule set. rp-ccCA is a pseudopotential-based composite method for transition metals and is shown to yield accurate thermodynamic results for molecules containing heavy elements Ga-Kr and Y-Cd.
ISSN:1089-7690
DOI:10.1063/1.3662415