which depend also on concentrations. Microkinetic modeling, consisting of the
construction of explicit kinetic reaction networks, merges the rate constants provided
by calculations to reproduce the time evolution of the reaction species; it generates
data directly comparable to the experiment. The goal of the chapter “DFT-Based
Microkinetic Simulations: A Bridge Between Experiment and Theory in Synthetic
Chemistry,” by Prof. M. Jaraíz, is to enable the reader to carry out microkinetic
modeling and simulation studies of organometallic reactions, assuming the availability of a set of DFT energy values for the reaction rates involved.
To gain quantitative insight into the reactivity trends in organometallic chemistry,
in the chapter “A Quantitative Approach to Understanding Reactivity in Organometallic Chemistry” Prof. I. Fernández shows that reaction energy profiles are the base
for the application of activation strain model (ASM) and energy decomposition
analysis (EDA) methods. In this way a deeper understanding of the physical factors
controlling the reactivity can be achieved.
The next three chapters show how computational chemistry can be applied to
understanding new photocatalytic processes, performing ligand design in asymmetric catalysis, or studying how spin states of the complexes modulate their reactivity.
Photoactivated processes play an increasingly important role in chemistry, but the
accurate computational characterization of the photoexcitation of the chromophore
compounds and the reactivity of the excited state are challenging. In the chapter
“Computational Modeling of Selected Photoactivated Processes,” Prof. F. Maseras
shows that the application of TD-DFT calculations for the photoactivation step and
of conventional DFT calculations for selected regions of the potential energy surface
is a powerful approach for mechanistic understanding of such processes.
In the chapter “Ligand Design for Asymmetric Catalysis: Combining Mechanistic and Chemoinformatics Approaches,” Prof. R. Paton describes new methods to
accelerate the experimental screening process for developing asymmetric catalysts;
they show how calculations can guide experiments.
Despite the success of DFT methods for reactions involving closed-shell species,
DFT calculations of systems in which more than one spin state can be involved are
much more challenging. Chapter “Dealing with Spin States in Computational
Organometallic Catalysis,” by Prof. M. Swart, presents a detailed account of challenges posed by spin states in computational organometallic chemistry.
Modifying and fine-tuning organometallic catalysts requires an in-depth understanding of the complex metal–ligand (ML) interactions playing a key role in
determining the properties of organometallic compounds. In the chapter “Characterizing the Metal Ligand Bond Strength via Vibrational Spectroscopy: The Metal
Ligand Electronic Parameter MLEP,” Prof. E. Kraka introduces the metal–ligand
electronic parameter (MLEP), which is based on the local vibrational ML stretching
force constant and that is ideally suited to set up a scale of bond strength orders.
The chapters included in this volume give a general overview on how to generate
and critically analyze reaction mechanisms employing and combining modern
computational techniques. Moreover, some chapters also include reaction types
that were not reliably affordable not too long ago. Theoretical methods are mature
enough to be successfully applied to the field, though there is still room for the
vi
Preface
construction of explicit kinetic reaction networks, merges the rate constants provided
by calculations to reproduce the time evolution of the reaction species; it generates
data directly comparable to the experiment. The goal of the chapter “DFT-Based
Microkinetic Simulations: A Bridge Between Experiment and Theory in Synthetic
Chemistry,” by Prof. M. Jaraíz, is to enable the reader to carry out microkinetic
modeling and simulation studies of organometallic reactions, assuming the availability of a set of DFT energy values for the reaction rates involved.
To gain quantitative insight into the reactivity trends in organometallic chemistry,
in the chapter “A Quantitative Approach to Understanding Reactivity in Organometallic Chemistry” Prof. I. Fernández shows that reaction energy profiles are the base
for the application of activation strain model (ASM) and energy decomposition
analysis (EDA) methods. In this way a deeper understanding of the physical factors
controlling the reactivity can be achieved.
The next three chapters show how computational chemistry can be applied to
understanding new photocatalytic processes, performing ligand design in asymmetric catalysis, or studying how spin states of the complexes modulate their reactivity.
Photoactivated processes play an increasingly important role in chemistry, but the
accurate computational characterization of the photoexcitation of the chromophore
compounds and the reactivity of the excited state are challenging. In the chapter
“Computational Modeling of Selected Photoactivated Processes,” Prof. F. Maseras
shows that the application of TD-DFT calculations for the photoactivation step and
of conventional DFT calculations for selected regions of the potential energy surface
is a powerful approach for mechanistic understanding of such processes.
In the chapter “Ligand Design for Asymmetric Catalysis: Combining Mechanistic and Chemoinformatics Approaches,” Prof. R. Paton describes new methods to
accelerate the experimental screening process for developing asymmetric catalysts;
they show how calculations can guide experiments.
Despite the success of DFT methods for reactions involving closed-shell species,
DFT calculations of systems in which more than one spin state can be involved are
much more challenging. Chapter “Dealing with Spin States in Computational
Organometallic Catalysis,” by Prof. M. Swart, presents a detailed account of challenges posed by spin states in computational organometallic chemistry.
Modifying and fine-tuning organometallic catalysts requires an in-depth understanding of the complex metal–ligand (ML) interactions playing a key role in
determining the properties of organometallic compounds. In the chapter “Characterizing the Metal Ligand Bond Strength via Vibrational Spectroscopy: The Metal
Ligand Electronic Parameter MLEP,” Prof. E. Kraka introduces the metal–ligand
electronic parameter (MLEP), which is based on the local vibrational ML stretching
force constant and that is ideally suited to set up a scale of bond strength orders.
The chapters included in this volume give a general overview on how to generate
and critically analyze reaction mechanisms employing and combining modern
computational techniques. Moreover, some chapters also include reaction types
that were not reliably affordable not too long ago. Theoretical methods are mature
enough to be successfully applied to the field, though there is still room for the
vi
Preface