Segmented Gaussian Base Sets for All Electrons for He, Ca, Sr, Ba and Lanthanides.

Name: Igor Badke Ferreira
Type: PhD thesis
Publication date: 29/11/2019
Advisor:

Namesort descending Role
Francisco Elias Jorge Advisor *

Examining board:

Namesort descending Role
Antônio Canal Neto Internal Examiner *
Francisco Elias Jorge Advisor *
Giuseppi Gava Camiletti External Examiner *
João Pedro Braga External Examiner *
Rogério Custódio External Examiner *

Summary: Non-relativistic and Douglas-Kroll-Hess (DKH) augmented basis sets for He, Ca, Sr, Ba, and lanthanides are generated. These sets are appropriated to describe electrons away from the nuclei. Using the DKH augmented sets along with the B3LYP functional, bond lengths, dissociation energies, harmonic vibrational frequencies, adiabatic ionization potentials (Adiabatic Ionization Potencial, AIP) and electron affinities (Adiabatic Electron Affinity, AEA), and electric dipole moments for CaH, SrH, and BaH are computed. These results agree well with the most recent experimental and benchmark theoretical data published in the literature. The mean dipole polarizabilities reported in this work for some elements are close to the recommended values.
Nonrelativistic and relativistic DKH segmented all-electron Gaussian basis sets of valence triple zeta quality plus polarization functions (TZP) for the lanthanides are developed. As some atomic and molecular properties depend on a good description of the electrons far from the nuclei, these basis sets are augmented with diffuse functions, giving rise to the augmented TZP (ATZP) and ATZP-DKH basis sets. At the DKH level of theory, the B3LYP hybrid functional in conjunction with the TZP-DKH basis set are used to calculate the atomic charges and valence orbital populations of the lanthanide and oxygen atoms, equilibrium bond lengths, and dissociation energies of the lanthanide monoxides. The DKH-B3LYP/ATZP-DKH polarizability of Yb and the DKH-M06/TZP-DKH first ionization energies of the lanthanides are also reported. Compared with the values obtained with a larger all-electron basis set and with theoretical and experimental data found in the literature, the results obtained by our compact basis sets are verified to be accurate and reliable. Unlike effective core potential valence basis sets, our basis sets can also be employed in molecular property calculations that involve the simultaneous treatment of core and valence electrons.

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