Gaussian basis sets of quadruple zeta valence quality for Rb-Rn are presented, as well as bases of split valence and triple zeta valence quality for H-Rn. The latter were obtained by (partly) modifying bases developed previously. A large set of more than 300 molecules representing (nearly) all elements-except lanthanides-in their common oxidation states was used to assess the quality of the bases all across the periodic table. Quantities investigated were atomization energies, dipole moments and structure parameters for Hartree-Fock, density functional theory and correlated methods, for which we had chosen Moller-Plesset perturbation theory as an example. Finally recommendations are given which type of basis set is used best for a certain level of theory and a desired quality of results.

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy

Multiwfn is a multifunctional program for wavefunction analysis. Its main functions are: (1) Calculating and visualizing real space function, such as electrostatic potential and electron localization function at point, in a line, in a plane or in a spatial scope. (2) Population analysis. (3) Bond order analysis. (4) Orbital composition analysis. (5) Plot density-of-states and spectrum. (6) Topology analysis for electron density. Some other useful utilities involved in quantum chemistry studies are also provided. The built-in graph module enables the results of wavefunction analysis to be plotted directly or exported to high-quality graphic file. The program interface is very user-friendly and suitable for both research and teaching purpose. The code of Multiwfn is substantially optimized and parallelized. Its efficiency is demonstrated to be significantly higher than related programs with the same functions. Five practical examples involving a wide variety of systems and analysis methods are given to illustrate the usefulness of Multiwfn. The program is free of charge and open-source. Its precompiled file and source codes are available from http://multiwfn.codeplex.com.

Multiwfn: a multifunctional wavefunction analyzer.

We present an analysis of the performances of a parameter free density functional model (PBE0) obtained combining the so called PBE generalized gradient functional with a predefined amount of exact exchange. The results obtained for structural, thermodynamic, kinetic and spectroscopic (magnetic, infrared and electronic) properties are satisfactory and not far from those delivered by the most reliable functionals including heavy parameterization. The way in which the functional is derived and the lack of empirical parameters fitted to specific properties make the PBE0 model a widely applicable method for both quantum chemistry and condensed matter physics.

Toward reliable density functional methods without adjustable parameters: The PBE0 model

Recent extensions of the DMol3 local orbital density functional method for band structure calculations of insulating and metallic solids are described. Furthermore the method for calculating semilocal pseudopotential matrix elements and basis functions are detailed together with other unpublished parts of the methodology pertaining to gradient functionals and local orbital basis sets. The method is applied to calculations of the enthalpy of formation of a set of molecules and solids. We find that the present numerical localized basis sets yield improved results as compared to previous results for the same functionals. Enthalpies for the formation of H, N, O, F, Cl, and C, Si, S atoms from the thermodynamic reference states are calculated at the same level of theory. It is found that the performance in predicting molecular enthalpies of formation is markedly improved for the Perdew–Burke–Ernzerhof [Phys. Rev. Lett. 77, 3865 (1996)] functional.

From molecules to solids with the DMol3 approach

We present the theoretical and technical foundations of the Amsterdam Density Functional (ADF) program with a survey of the characteristics of the code (numerical integration, density fitting for the Coulomb potential, and STO basis functions). Recent developments enhance the efficiency of ADF (e.g., parallelization, near order-N scaling, QM/MM) and its functionality (e.g., NMR chemical shifts, COSMO solvent effects, ZORA relativistic method, excitation energies, frequency-dependent (hyper)polarizabilities, atomic VDD charges). In the Applications section we discuss the physical model of the electronic structure and the chemical bond, i.e., the Kohn–Sham molecular orbital (MO) theory, and illustrate the power of the Kohn–Sham MO model in conjunction with the ADF-typical fragment approach to quantitatively understand and predict chemical phenomena. We review the “Activation-strain TS interaction” (ATS) model of chemical reactivity as a conceptual framework for understanding how activation barriers of various types of (competing) reaction mechanisms arise and how they may be controlled, for example, in organic chemistry or homogeneous catalysis. Finally, we include a brief discussion of exemplary applications in the field of biochemistry (structure and bonding of DNA) and of time-dependent density functional theory (TDDFT) to indicate how this development further reinforces the ADF tools for the analysis of chemical phenomena. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 931–967, 2001

Chemistry with ADF

https://www.lct.jussieu.fr/pagesperso/savin/papers/lyp/MieSavStoPre-89.pdf

Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr

Nonrelativistic and quasirelativistic ab‐initio pseudopotentials representing the Ne‐like X(Z−10)+ cores (X=Sc–Zn) of the first row transition metals and optimized (8s7p6d1f )/[6s5p3d1f ]‐GTO valence basis sets for use in molecular calculations have been generated. Excitation and ionization energies of the low lying states of Sc through Zn from numerical HF‐ as well as SCF‐ and CI(SD)‐pseudopotential calculations using the derived basis sets differ by less than 0.1 eV from corresponding all‐electron results.

Energy‐adjusted ab initio pseudopotentials for the first row transition elements

We present nonrelativistic and quasirelativistic energy‐adjusted pseudopotentials, the latter augmented by spin–orbit operators, as well as optimized (12s11p10d8f)/ [8s7p6d4f]‐Gaussian‐type orbitals (GTO) valence basis sets for the actinide elements actinium through lawrencium. Atomic excitation and ionization energies obtained by the use of these pseudopotentials and basis sets in self‐consistent field (SCF) calculations differ by less than 0.2 eV from corresponding finite‐difference all‐electron results. Large‐scale multiconfiguration self‐consistent field (MCSCF), multireference configuration interaction (MRCI), and multireference averaged coupled‐pair functional (MRACPF) calculations for thorium and thorium monoxide yield results in satisfactory agreement with available experimental data. Preliminary results from spin–orbit configuration interaction calculations for the low‐lying electronic states of thorium monoxide are also reported.

Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide

Nonrelativistic and quasirelativistic energy-adjusted pseudopotentials and optimized (7s6p5d)/[5s4p3d]-GTO valence basis sets for use in molecular calculations for fixed f-subconfigurations of the rare earth elements, La through Lu, have been generated. Atomic excitation and ionization energies from numerical HF, as well as SCF pseudopotential calculations using the derived basis sets, differ by less than 0.1 eV from numerical HF all-electron results. Corresponding values obtained from CI(SD), CEPA-1, as well as density functional calculations using the quasirelativistic pseudopotentials, are in reasonable agreement with experimental data.

/pdf/energy-adjusted-pseudopotentials-for-the-rare-earth-elements-dgn8smf2vu.pdf

Energy-adjusted pseudopotentials for the rare earth elements

Nonrelativistic and quasirelativistic energy‐adjusted ab initio pseudopotentials substituting the 1s–3d core orbitals with corresponding spin–orbit operators for the rare earth elements Ce through Yb have been generated. Excitation and ionization energies from numerical pseudopotential calculations differ by less than 0.1 eV from corresponding numerical all–electron results. The pseudopotentials for Ce have been tested in molecular calculations for the 3Φ ground state of CeO. The derived spectroscopic constants from quasirelativistic pseudopotential CI(SD) calculations including Davidson’s correction (Re=1.827 A, De=6.95 eV, ωe=834 cm−1) are in good agreement with experimental values (Re=1.820 A, De=8.19 eV, ωe=862 cm−1).

Heinzwerner Preuss

Papers

Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr

Energy‐adjusted ab initio pseudopotentials for the first row transition elements

Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide

Energy-adjusted pseudopotentials for the rare earth elements

Energy‐adjusted ab initio pseudopotentials for the rare earth elements