Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order Møller-Plesset perturbation theory, fourth-order Møller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+ 1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values

Iowa's Adult Basic Education Program Annual Benchmark Report Executive Summary, 2002

The purpose of this publication is to present the Executive Summary for the Program Year 2002 report on Iowa’s adult basic education program benchmarks. The passage of the Workforce Investment Act (WIA) of 1998 [Public Law 105-220] by the 105th Congress has ushered in a new era of collaboration, coordination, cooperation and accountability. The overall goal of the Act is “to increase the employment, retention, and earnings of participants, and increase occupational skill attainment by participants, and, as a result improve the quality of the workforce, reduce welfare dependency, and enhance the productivity and competitiveness of the Nation.”

Iowa's Adult Basic Education Program Annual Benchmark Report, 2002

One of the major intents of AEFLA was to establish performance measures and benchmarks to demonstrate increased accountability in line with the major goals and objectives of WIA. Section 212(2)(A) of the Act specifies that each eligible agency (e.g. The Iowa Department of Education) is subject to certain core indicators of performance and has the authority to specify additional indicators.

Iowa's Adult Basic Education Program Annual Benchmark Report Executive Summary, 2001

The purpose of this publication is to present the Executive Summary of the first annual report on the results of Iowa’s adult basic education program benchmarks. The passage of the Workforce Investment Act (WIA) of 1998 [Public Law 105-220] by the 105th Congress has ushered in a new era of collaboration, coordination, cooperation and accountability. The overall goal of the Act is “to increase the employment, retention, and earnings of participants, and increase occupational skill attainment by participants, and, as a result improve the quality of the workforce, reduce welfare dependency, and enhance the productivity and competitiveness of the Nation.”

Iowa's Adult Basic Education Program Annual Benchmark Report, 2001

The purpose of Title II, The Adult Education and Family Literacy Act (AEFLA) of the Workforce Investment Act of 1998, is to create a partnership among the federal government, states, and localities to provide, on a voluntary basis, adult basic education and literacy services.

Iowa Adult Literacy Program Annual Benchmark Report, 2003

The purpose of Title II, The Adult Education and Family Literacy Act (AEFLA) of the Workforce Investment Act of 1998, is to create a partnership among the federal government, states, and localities to provide, on a voluntary basis, adult basic education and literacy services.

Iowa's Adult Literacy Program Benchmark Analysis Report, 2002

The purpose of this document is to present Iowa’s Adult Literacy Benchmark Analysis Report: Program Year 2002. The report is designed to provide a supplemental analysis of the information presented in Tables 5-19 (pp. 16-37) referenced in the publication titled Iowa's Adult Basic Education Program Annual Benchmark Report: Program Year 2002. The original data source for Tables 1-7 is from Iowa’s National Reporting System (NRS) report Tables 4B and 5 and the publication titled Iowa’s Community College Basic Literacy Skills Credential Program: Program Year 2002. (See Appendix B of Iowa’s Adult Basic Education Program Annual Benchmark Report: Program Year 2002, [pp. 54-55] and Iowa’s Community College Basic Literacy Skills Credential Program Annual Report: Program Year 2002 Tables 1-2 [pp. 6-7]).

Iowa Adult Basic Education Program Benchmark Objective for Program Year, 2002

The benchmark objectives for Program Year 2002 are designed to improve Iowa's basic skills literacy program in those instructional programs, educational functioning levels, and follow-up categories which did not achieve the negotiated benchmark levels for Program Year 2001. The instructional programs, educational functioning levels and follow-up categories in which the attained benchmarks met or exceeded the negotiated benchmarks for Program Year 2001 should not be allowed to fall below the Program Year 2001 levels for Program Year 2002.

Iowa’s Adult Literacy Program Annual Benchmark Report Executive Summary, 2004

This report was produced by the Iowa Department of Education about Adult Literacy.

Iowa’s Adult Literacy Program Benchmark Projection Report, 2004

This report was produced by the Iowa Department of Education about Adult Literacy.

Iowa Adult Literacy Program Annual Benchmark Report, 2005

The purpose of this publication is to present the Program Year 2005 report on Iowa’s adult literacy program benchmarks. The passage of the Workforce Investment Act (WIA) of 1998 [Public Law 105-220] by the 105th Congress ushered in a new era of collaboration, coordination, cooperation and accountability. The overall goal of the Act is “to increase the employment, retention, and earnings of participants, and increase occupational skill attainment by participants, and, as a result improve the quality of the workforce, reduce welfare dependency, and enhance the productivity and competitiveness of the Nation.”

Iowa's Adult Basic Education Program Annual Benchmark Report Executive Summary, 2005

The purpose of this publication is to present the Executive Summary for the Program Year 2002 report on Iowa’s adult basic education program benchmarks. The passage of the Workforce Investment Act (WIA) of 1998 [Public Law 105-220] by the 105th Congress has ushered in a new era of collaboration, coordination, cooperation and accountability. The overall goal of the Act is “to increase the employment, retention, and earnings of participants, and increase occupational skill attainment by participants, and, as a result improve the quality of the workforce, reduce welfare dependency, and enhance the productivity and competitiveness of the Nation.”

Iowa Adult Literacy Program Benchmark Presentation, 2005

The purpose of this publication is to present the Executive Summary Program Year 2005 report on Iowa’s adult literacy program benchmarks.1 The passage of the Workforce Investment Act (WIA) of 1998 [Public Law 105-220] by the 105th Congress ushered in a new era of collaboration, coordination, cooperation and accountability. The overall goal of the Act is “to increase the employment, retention, and earnings of participants, and increase occupational skill attainment by participants, and, as a result improve the quality of the workforce, reduce welfare dependency, and enhance the productivity and competitiveness of the Nation.”

Iowa's Adult Literacy Program Annual Benchmark Report, 2006

The purpose of this publication is to present the Program Year 2006 report on Iowa’s adult literacy program benchmarks. The passage of the Workforce Investment Act (WIA) of 1998 [Public Law 105-220] by the 105th Congress ushered in a new era of collaboration, coordination, cooperation and accountability. The overall goal of the Act is “to increase the employment, retention, and earnings of participants, and increase occupational skill attainment by participants, and, as a result improve the quality of the workforce, reduce welfare dependency, and enhance the productivity and competitiveness of the Nation.”