title: A pseudopotential-based composite method: the relativistic pseudopotential correlation consistent composite approach for molecules containing 4d transition metals (Y-Cd).
abstract: 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.
authors.affiliation: Center for Advanced Scientific Computing and Modeling (CASCaM), Department of Chemistry, University of North Texas, Denton, Texas 76203-5070, USA.
authors.forename: Marie L
authors.initials: ML
authors.lastname: Laury
authors.forename: Nathan J
authors.initials: NJ
authors.lastname: DeYonker
authors.forename: Wanyi
authors.initials: W
authors.lastname: Jiang
authors.forename: Angela K
authors.initials: AK
authors.lastname: Wilson
mesh_terms: D003198:Computer Simulation; D008956:Models, Chemical; D011789:Quantum Theory; D013816:Thermodynamics; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D028561:Transition Elements