Top Organomet Chem (2020) 67: 81–106
https://doi.org/10.1007/3418_2020_44
# Springer Nature Switzerland AG 2020
Published online: 11 July 2020
DFT-Based Microkinetic Simulations: A
Bridge Between Experiment and Theory
in Synthetic Chemistry
Martín Jaraíz
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2 Identification of Mechanisms: Experimental Tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3 Calculation of DFT Energies: Theoretical Tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
4 Running Kinetic Simulations: A Brief Tutorial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5 Case Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
5.1 Example 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
5.2 Example 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Abstract The goal of this chapter is to enable the reader to carry out microkinetic
modeling and simulation studies of synthetic chemistry problems, assuming the
availability of a set of DFT energy values for the reaction rates involved. To this
end, after a brief introduction, we describe the tools that we use and the modeling
methodology that we follow and then provide a short tutorial and input files for the
microkinetic simulator that we normally use (available free of charge). Finally, we
analyze two case examples to show the remarkable level of insight and prediction
power attainable with this DFT-based microkinetic modeling methodology.
Keywords DFT · Mechanism · Microkinetic · Modeling · Reaction rate · Simulation
Electronic supplementary material The online version of this chapter (https://doi.org/10.1007/
3418_2020_44) contains supplementary material, which is available to authorized users.
M. Jaraíz (*)
Department of Electronics, University of Valladolid, Valladolid, Spain
e-mail: mjaraiz@ele.uva.es
https://doi.org/10.1007/3418_2020_44
# Springer Nature Switzerland AG 2020
Published online: 11 July 2020
DFT-Based Microkinetic Simulations: A
Bridge Between Experiment and Theory
in Synthetic Chemistry
Martín Jaraíz
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2 Identification of Mechanisms: Experimental Tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3 Calculation of DFT Energies: Theoretical Tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
4 Running Kinetic Simulations: A Brief Tutorial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5 Case Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
5.1 Example 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
5.2 Example 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
Abstract The goal of this chapter is to enable the reader to carry out microkinetic
modeling and simulation studies of synthetic chemistry problems, assuming the
availability of a set of DFT energy values for the reaction rates involved. To this
end, after a brief introduction, we describe the tools that we use and the modeling
methodology that we follow and then provide a short tutorial and input files for the
microkinetic simulator that we normally use (available free of charge). Finally, we
analyze two case examples to show the remarkable level of insight and prediction
power attainable with this DFT-based microkinetic modeling methodology.
Keywords DFT · Mechanism · Microkinetic · Modeling · Reaction rate · Simulation
Electronic supplementary material The online version of this chapter (https://doi.org/10.1007/
3418_2020_44) contains supplementary material, which is available to authorized users.
M. Jaraíz (*)
Department of Electronics, University of Valladolid, Valladolid, Spain
e-mail: mjaraiz@ele.uva.es