Ensemble of segmented Gaussian bases for all the electrons of the elements from Cs to Rn and from Th to Lr.

Name: Lucas Sousa Carvalho Martins
Type: PhD thesis
Publication date: 06/02/2017
Advisor:

Namesort descending Role
Francisco Elias Jorge Advisor *

Examining board:

Namesort descending Role
Antônio Canal Neto Internal Examiner *
Francisco Elias Jorge Advisor *
Jair Carlos Checon de Freitas Internal Examiner *
Luiz Carlos Machado External Examiner *
Nelson Henrique Morgon External Examiner *

Summary: All-electron contracted Gaussian basis set of triple zeta valence quality plus polarization functions (TZP) for the elements Cs, Ba, La, and from Hf to Rn is presented. Douglas-Kroll-Hess (DKH) basis set for fifth-row elements is also reported. We have recontracted the original TZP basis set, i.e., the values of the contraction coefficients are re-optimized using the second-order DKH Hamiltonian. By addition of diffuse functions (s, p, d, f, and g symmetries), which are optimized for the anion ground states, an augmented TZP basis set is constructed. Using the Becke 3-parameter (exchange) and the Lee, Yang and Parr (correlation) functional (B3LYP), the performance of the TZP-DKH basis set is assessed for predicting atomic ionization energy as well as spectroscopy constants of some compounds.
Segmented all-electron basis sets of valence double zeta quality plus polarization functions (DZP) for the elements from Ce to Lu are also generated to be used with the non-relativistic and DKH Hamiltonians. At the B3LYP level, the DZP-DKH atomic ionization energies and equilibrium bond lengths and atomization energies of the lanthanide trifluorides are evaluated and compared with benchmark theoretical and experimental data reported in the literature.
Finally, for the actinides, two segmented all-electron basis sets of valence double zeta quality plus polarization functions (DZP) are developed. One of them must be used along with the non-relativistic Hamiltonian, WHEREas the other with the DKH one. For the actinide trichlorides, geometric parameters, atomic charges of the actinides, and populations for the actinide valence orbitals are calculated using the B3LYP functional in conjunction with the DZP-DKH basis set. For UCl3 and UF3, dissociation energies are also reported. Comparison with benchmark theoretical and experimental values found in the literature is carried out.
It is verified that the performance of the relativistic compact size basis sets generated in this work are regular, efficient, and reliable. They will be extremely helpful on molecular property calculations that need explicitly to consider the core electrons.

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