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The Importance of the Density Functional Theory Exchange-Correlation Hartree-Fock Term in Magnetic Resonance: Application to an Aqueous Environment.
Provasi, Patricio F; Modesto-Costa, Lucas; Sampaio, Felipe; Silva, Tércio; da Cunha, Antônio R; Andrade-Filho, Tarciso; Gester, Rodrigo.
Afiliação
  • Provasi PF; Department of Physics, IMIT, Northeastern University, CONICET, AV. Libertad 5500, W 3404 AAS Corrientes, Argentina.
  • Modesto-Costa L; Departamento de Física, Universidade Federal Rural do Rio de Janeiro, Seropédica, RJ 23890-000, Brazil.
  • Sampaio F; Departamento de Química, Instituto Militar de Engenharia (IME), Rio de Janeiro, RJ 22290-270, Brazil.
  • Silva T; Programa de Pós-Graduação em Química, Universidade Federal do Sul e Sudeste do Pará, Marabá, PA68507-590, Brazil.
  • da Cunha AR; Programa de Pós-Graduação em Química, Universidade Federal do Sul e Sudeste do Pará, Marabá, PA68507-590, Brazil.
  • Andrade-Filho T; Ciências Naturais, Universidade do Estado do Pará, Belém, PA 66095-015, Brazil.
  • Gester R; Universidade Federal do Maranhão, UFMA, Campus Balsas, Maranhão CEP 65800-000, Brazil.
J Phys Chem A ; 127(3): 619-626, 2023 Jan 26.
Article em En | MEDLINE | ID: mdl-36648308
Within the framework of Density Functional Theory (DFT), the relevance of the term Hartree-Fock exchange (HFE) for a variety of molecular properties is a critical point. For this reason, we spend efforts to understand these relationships in nuclear magnetic resonance (NMR) parameters in a water solvent. This work takes advantage of the appropriate aug-cc-pVTZ-J basis set and the Minnesota family of DFT methods, which consider different portions of HFE contributions. With regard to solvent participation, the results are based on a sequential Monte Carlo/Quantum Mechanics procedure, which builds the structures of the liquid under realistic thermodynamic conditions. Compared to the accurate results of second-order polarization propagator approximation (SOPPA) and experimental data, all NMR parameters show a huge dependence on the size of the HFE contribution. For instance, the inclusion of this term in 1JOH and 2JHH indirect spin-spin couplings does vary with 49.661 and 25.459 Hz, respectively. The M06-HF method accounts for 100% of HFE and better matches the σO and σH shielding constants. On the other hand, 1JOH and 2JHH demand a medium contribution (54% of HFE), the best description being associated with the M06-2X method. Thus, the dependence varies regarding the phenomenology of the property in focus and the order for independent treatments. For elements that participate in hydrogen bonds simultaneously as donor and acceptor actors, the results indicate that explicit solvent molecules must be considered in the quantum mechanical calculations for better modeling of paramagnetic shielding constants.
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Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Tipo de estudo: Qualitative_research Idioma: En Revista: J Phys Chem A Assunto da revista: QUIMICA Ano de publicação: 2023 Tipo de documento: Article País de afiliação: Argentina País de publicação: Estados Unidos
Texto completo
Adicionar na Minha BVS
Imprimir
XML
PubMed Links
Buscar no Google

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Tipo de estudo: Qualitative_research Idioma: En Revista: J Phys Chem A Assunto da revista: QUIMICA Ano de publicação: 2023 Tipo de documento: Article País de afiliação: Argentina País de publicação: Estados Unidos