Thermodynamic Properties of Gaseous Ruthenium ...
Document type :
Article dans une revue scientifique
DOI :
Permalink :
Title :
Thermodynamic Properties of Gaseous Ruthenium Species
Author(s) :
Miradji, Faoulat [Auteur]
Laboratoire de Recherche commun IRSN-CNRS-Lille1 "Cinétique Chimique, Combustion, Réactivité" [C3R]
Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
Souvi, Sidi [Auteur]
Laboratoire de Recherche commun IRSN-CNRS-Lille1 "Cinétique Chimique, Combustion, Réactivité" [C3R]
Institut de Radioprotection et de Sûreté Nucléaire [IRSN]
Cantrel, Laurent [Auteur]
Laboratoire de Recherche commun IRSN-CNRS-Lille1 "Cinétique Chimique, Combustion, Réactivité" [C3R]
Institut de Radioprotection et de Sûreté Nucléaire [IRSN]
LOUIS, Florent [Auteur]
Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
Vallet, Valérie [Auteur]
Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 [PhLAM]
Laboratoire de Recherche commun IRSN-CNRS-Lille1 "Cinétique Chimique, Combustion, Réactivité" [C3R]
Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
Souvi, Sidi [Auteur]
Laboratoire de Recherche commun IRSN-CNRS-Lille1 "Cinétique Chimique, Combustion, Réactivité" [C3R]
Institut de Radioprotection et de Sûreté Nucléaire [IRSN]
Cantrel, Laurent [Auteur]
Laboratoire de Recherche commun IRSN-CNRS-Lille1 "Cinétique Chimique, Combustion, Réactivité" [C3R]
Institut de Radioprotection et de Sûreté Nucléaire [IRSN]
LOUIS, Florent [Auteur]
Physicochimie des Processus de Combustion et de l’Atmosphère - UMR 8522 [PC2A]
Vallet, Valérie [Auteur]
Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 [PhLAM]
Journal title :
Journal of Physical Chemistry. Part A
Abbreviated title :
J. Phys. Chem. A
Volume number :
119
Pages :
4961-4971
Publication date :
2015-04
English keyword(s) :
Ruthenium
Oxides
Quantum mechanics
Chemical calculations
Enthalpy
Oxides
Quantum mechanics
Chemical calculations
Enthalpy
HAL domain(s) :
Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
English abstract : [en]
The review of thermodynamic data of ruthenium oxides reveals large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce ...
Show more >The review of thermodynamic data of ruthenium oxides reveals large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. The reaction energies leading to the formation of ruthenium oxides RuO, RuO2, RuO3, and RuO4 have been calculated for a series of reactions. The combination of different quantum chemical methods has been investigated [DFT, CASSCF, MRCI, CASPT2, CCSD(T)] in order to predict the geometrical parameters, the energetics including electronic correlation and spin–orbit coupling. The most suitable method for ruthenium compounds is the use of TPSSh-5%HF for geometry optimization, followed by CCSD(T) with complete basis set (CBS) extrapolations for the calculation of the total electronic energies. SO-CASSCF seems to be accurate enough to estimate spin–orbit coupling contributions to the ground-state electronic energies. This methodology yields very accurate standard enthalpies of formations of all species, which are either in excellent agreement with the most reliable experimental data or provide an improved estimate for the others. These new data will be implemented in the thermodynamical databases that are used by the ASTEC code (accident source term evaluation code) to build models of ruthenium chemistry behavior in severe nuclear accident conditions. The paper also discusses the nature of the chemical bonds both from molecular orbital and topological view points.Show less >
Show more >The review of thermodynamic data of ruthenium oxides reveals large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. The reaction energies leading to the formation of ruthenium oxides RuO, RuO2, RuO3, and RuO4 have been calculated for a series of reactions. The combination of different quantum chemical methods has been investigated [DFT, CASSCF, MRCI, CASPT2, CCSD(T)] in order to predict the geometrical parameters, the energetics including electronic correlation and spin–orbit coupling. The most suitable method for ruthenium compounds is the use of TPSSh-5%HF for geometry optimization, followed by CCSD(T) with complete basis set (CBS) extrapolations for the calculation of the total electronic energies. SO-CASSCF seems to be accurate enough to estimate spin–orbit coupling contributions to the ground-state electronic energies. This methodology yields very accurate standard enthalpies of formations of all species, which are either in excellent agreement with the most reliable experimental data or provide an improved estimate for the others. These new data will be implemented in the thermodynamical databases that are used by the ASTEC code (accident source term evaluation code) to build models of ruthenium chemistry behavior in severe nuclear accident conditions. The paper also discusses the nature of the chemical bonds both from molecular orbital and topological view points.Show less >
Language :
Anglais
Audience :
Internationale
Popular science :
Non
Administrative institution(s) :
Université de Lille
CNRS
CNRS
Collections :
Research team(s) :
Cinétique chimique, Combustion, Réactivité (C3R) : Sûreté Nucléaire
Submission date :
2018-11-27T14:37:23Z
2020-10-05T10:57:45Z
2020-10-05T10:57:45Z