Catalytic Properties of Selected
Transition Metal
Oxides—Computational Studies
Witold Piskorz and Filip Zasada
Abstract This chapter is the review of the computational methods applied to the
transition metal oxides most abundant in heterogeneous catalysis and is focused
on the influence of the environment on the transition metal cation properties. The
shortcomings of the most commonly used DFT level of theory are discussed, and
its extensions towards more realistic environment are presented. The modern reactive force-field methods are also mentioned. The embedding schemes most commonly found in the quantum-chemical or classical description of the heterogeneous
processes are discussed. The errors stemming from the non-completeness of the
basis function, i.e. the basis set superposition error, found in the calculations with
atomic basis, and the Pulay stress, occurring in the planewave calculations, together
with remedies, are briefly described. It is shown that in all discussed systems, i.e.
CeO 2 , TiO 2 , ZrO 2 , zeolites, d-electron metal spinels, and V 2 O 5 , the appropriately
applied Hubbard DFT GGA+U methods are successful for the compromise between
computational cost and resultant accuracy. The much more time-consuming hybrid
functionals give slightly more accurate results and, moreover, are more universal in
the sense that they do not need calibration against experiment contrary to DFT+U
where the Hubbard correction needs to be carefully selected for modelling particular
properties.
1 Introduction
Generally, the coordination environment term is considered as in the coordination
between ligand and central ion in the complex molecular compounds in, e.g., solutions in homogeneous catalysis [1, 2]. This term can be, however, applied also to the
solid state—the periodic (PBC, extended) systems, which can be locally, and in the
W. P. dedicates this work to his mother on the occasion of her round jubilee.
W. Piskorz (B) · F. Zasada
Faculty of Chemistry, Jagiellonian University, Kraków, Poland
e-mail: wpiskorz@chemia.uj.edu.pl
© Springer Nature Switzerland AG 2019
E. Broclawik et al. (eds.), Transition Metals in Coordination Environments,
Challenges and Advances in Computational Chemistry and Physics 29,
https://doi.org/10.1007/978-3-030-11714-6_12
345
Transition Metal
Oxides—Computational Studies
Witold Piskorz and Filip Zasada
Abstract This chapter is the review of the computational methods applied to the
transition metal oxides most abundant in heterogeneous catalysis and is focused
on the influence of the environment on the transition metal cation properties. The
shortcomings of the most commonly used DFT level of theory are discussed, and
its extensions towards more realistic environment are presented. The modern reactive force-field methods are also mentioned. The embedding schemes most commonly found in the quantum-chemical or classical description of the heterogeneous
processes are discussed. The errors stemming from the non-completeness of the
basis function, i.e. the basis set superposition error, found in the calculations with
atomic basis, and the Pulay stress, occurring in the planewave calculations, together
with remedies, are briefly described. It is shown that in all discussed systems, i.e.
CeO 2 , TiO 2 , ZrO 2 , zeolites, d-electron metal spinels, and V 2 O 5 , the appropriately
applied Hubbard DFT GGA+U methods are successful for the compromise between
computational cost and resultant accuracy. The much more time-consuming hybrid
functionals give slightly more accurate results and, moreover, are more universal in
the sense that they do not need calibration against experiment contrary to DFT+U
where the Hubbard correction needs to be carefully selected for modelling particular
properties.
1 Introduction
Generally, the coordination environment term is considered as in the coordination
between ligand and central ion in the complex molecular compounds in, e.g., solutions in homogeneous catalysis [1, 2]. This term can be, however, applied also to the
solid state—the periodic (PBC, extended) systems, which can be locally, and in the
W. P. dedicates this work to his mother on the occasion of her round jubilee.
W. Piskorz (B) · F. Zasada
Faculty of Chemistry, Jagiellonian University, Kraków, Poland
e-mail: wpiskorz@chemia.uj.edu.pl
© Springer Nature Switzerland AG 2019
E. Broclawik et al. (eds.), Transition Metals in Coordination Environments,
Challenges and Advances in Computational Chemistry and Physics 29,
https://doi.org/10.1007/978-3-030-11714-6_12
345