Banca de DEFESA: FELIPE CESAR TORRES ANTONIO

Uma banca de DEFESA de DOUTORADO foi cadastrada pelo programa.
DISCENTE : FELIPE CESAR TORRES ANTONIO
DATA : 28/07/2021
HORA: 14:00
LOCAL: https://meet.google.com/fhj-zuon-pgf
TÍTULO:

Density functional theory applied to theoretical studies of macrocycles

PÁGINAS: 92
GRANDE ÁREA: Ciências Exatas e da Terra
ÁREA: Química
SUBÁREA: Físico-Química
ESPECIALIDADE: Química Teórica
RESUMO:

The time-dependent and time-independent density functional theory (TD-DFT/DFT) were employed in the computational study of phthalocyanine, naphthalocyanine, and porphyrazin derivatives, aiming at deepening the understanding of the applicability as photosensitizers in photodynamic therapy. In this work, we have investigated the structural and electronic properties of species in the ground and excited states, as well as possible interactions with solvent molecules and self-aggregation. Hence, TD-DFT/DFT were employed to obtain ground and excited states geometries, vibrational frequencies, thermodynamic data, and absorption spectra. Furthermore, solvation effects were evaluated by means of both IEFPCM and COSMO continuous solvation methods. Furthermore, to better describe the long-range interactions, the D3BJ dispersion correction was employed. The solvatochromic effect was not entirely described by the continuous solvation models since there is a possibility of the solvent's coordination by the macrocycles' central metal. In the case of porphyrazines, solvent coordination and substituents increase the partial positive charge of the central metal leading to dye photobleaching. Asymmetric substitutions and the increase in the π-system for phthalocyanines and naphthalocyanines cause a redshift of the electronic absorption spectrum. Furthermore, conformational changes in the excited states in relation to the ground state are responsible for incrementing the generation of singlet oxygen of these compounds. Among the dimers found, the H-type is the most stable because the relative position of each monomer allows a closer approximation between the monomers and, consequently, more significant interaction between the π-systems. It was also possible to find J-type dimers when the lateral substituents facilitated hydrogen bond interactions. In addition, a benchmark was carried out to describe the electronic and energetic properties of polycyclic aromatic hydrocarbons and radicals. Also, in a collaboration, heterogeneous electrocatalysts applied to the ethanol oxidation reaction were studied.

MEMBROS DA BANCA:
Presidente - Interno ao Programa - 1544394 - PAULA HOMEM DE MELLO
Membro Titular - Examinador(a) Interno ao Programa - 149.405.258-05 - KATHIA MARIA HONORIO - USP
Membro Titular - Examinador(a) Externo à Instituição - ALINE THAÍS BRUNI - USP
Membro Titular - Examinador(a) Externo à Instituição - THIAGO TEIXEIRA TASSO - UFMG
Membro Titular - Examinador(a) Externo à Instituição - KLEBER THIAGO DE OLIVEIRA - UFSCAR
Membro Suplente - Examinador(a) Interno ao Programa - 1864481 - HUEDER PAULO MOISES DE OLIVEIRA
Membro Suplente - Examinador(a) Externo à Instituição - GABRIELA DIAS DA SILVA - USP
Membro Suplente - Examinador(a) Externo à Instituição - FERNANDA BETTANIN - USP