title: How computational methods and relativistic effects influence the study of chemical reactions involving Ru-NO complexes?
abstract: Two treatments of relativistic effects, namely effective core potentials (ECP) and all-electron scalar relativistic effects (DKH2), are used to obtain geometries and chemical reaction energies for a series of ruthenium complexes in B3LYP/def2-TZVP calculations. Specifically, the reaction energies of reduction (A-F), isomerization (G-I), and Cl-negative trans influence in relation to NH3(J-L) are considered. The ECP and DKH2 approaches provided geometric parameters close to experimental data and the same ordering for energy changes of reactions A-L. From geometries optimized with ECP, the electronic energies are also determined by means of the same ECP and basis set combined with the computational methods: MP2, M06, BP86, and its derivatives, so as B2PLYP, LC-wPBE, and CCSD(T) (reference method). For reactions A-I, B2PLYP provides the best agreement with CCSD(T) results. Additionally, B3LYP gave the smallest error for the energies of reactions J-L. © 2017 Wiley Periodicals, Inc.
authors.affiliation: Departamento de Química, FFCLRP, Universidade de São Paulo, Ribeirão Preto, SP, 14040-901, Brazil.
authors.forename: Renato Pereira
authors.initials: RP
authors.lastname: Orenha
authors.affiliation: Departamento de Química e Física Molecular, Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador São-carlense, 400-CP 780, São Carlos, SP, 13560-970, Brazil.
authors.forename: Régis Tadeu
authors.initials: RT
authors.lastname: Santiago
authors.affiliation: Departamento de Química e Física Molecular, Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador São-carlense, 400-CP 780, São Carlos, SP, 13560-970, Brazil.
authors.forename: Roberto Luiz Andrade
authors.initials: RL
authors.lastname: Haiduke
authors.affiliation: Departamento de Química, FFCLRP, Universidade de São Paulo, Ribeirão Preto, SP, 14040-901, Brazil.
authors.forename: Sérgio Emanuel
authors.identifier: 0000-0001-5018-4643
authors.initials: SE
authors.lastname: Galembeck
keywords: DKH2; computational thermochemistry; effective core potential; nitric oxide donors; relativistic effects