Atomic Scale Modelling of Electrochemical Systems 1st Edition by Marko Melander 9781119605614 111960561X

Part I:

1 Introduction to Atomic Scale Electrochemistry

1.1 Background

1.2 The thermodynamics of electrified interface

1.3 Chemical interactions between the electrode and redox species

1.4 Reaction kinetics at electrochemical interfaces

1.5 Charge transport

1.6 Mass transport to the electrode

1.7 Summary

References

Part II:

2 Retrospective and Prospective Views of Electrochemical Electron Transfer Processes: Theory and Computations

2.1 Introduction – interfacial molecular electrochemistry in recent retrospective

2.2 Analytical theory of molecular electrochemical ET processes

2.3 Ballistic and stochastic (Kramers‐Zusman) chemical rate theory

2.4 Early and recent views on chemical and electrochemical long‐range ET

2.5 Molecular‐scale electrochemical science

2.6 Computational approaches to electrochemical surfaces and processes revisited

2.7 Quantum and computational electrochemistry in retrospect and prospect

2.8 A few concluding remarks

Acknowledgement

References

Part III:

3 Continuum Embedding Models for Electrolyte Solutions in First‐Principles Simulations of Electrochemistry

3.1 Introduction to continuum models for electrochemistry

3.2 Continuum models of liquid solutions

3.3 Continuum diffuse‐layer models

3.4 Grand canonical simulations of electrochemical systems

3.5 Selected applications

Acknowledgments

References

Notes

4 Joint and grand‐canonical density‐functional theory

4.1 Introduction

4.2 JDFT variational theorem and framework

4.3 Classical DFT with atomic‐scale structure

4.4 Continuum solvation models from JDFT

4.5 Grand‐canonical DFT

4.6 Conclusions

References

Notes

5 Ab initio modeling of electrochemical interfaces and determination of electrode potentials

5.1 Introduction

5.2 Theoretical background of electrochemistry

5.3 Short survey of computational methods for modeling electrochemical interfaces

5.4 Ab initio determination of electrode potentials of electrochemical interfaces

5.5 Computation of potentials of zero charge

5.6 Summary

Acknowledgement

References

6 Molecular Dynamics of the Electrochemical Interface and the Double Layer

6.1 Introduction

6.2 Continuum description of the electric double layer

6.3 Equilibrium coverage of metal electrodes

6.4 First‐principles simulations of electrochemical interfaces and electric double layers

6.5 Electric double layers at battery electrodes

6.6 Conclusions

Acknowledgement

References

7 Atomic‐Scale Modelling of Electrochemical Interfaces through Constant Fermi Level Molecular Dynamics

7.1 Introduction

7.2 Method

7.3 CFL‐MD in aqueous solution: Determination of redox levels

7.4 CFL‐MD at metal‐water interface: The case of the Volmer reaction

7.5 Referencing the bias potential to the SHE

7.6 Macroscopic properties at the metal‐water interface

7.7 Atomic‐scale processes at the metal‐water interface

7.8 Conclusion

Acknowledgements

References

Note

Part IV:

8 From electrons to electrode kinetics: A tutorial review

8.1 Global electro‐neutrality

8.2 The electrochemical reference state

8.3 The chemical potential

8.4 The electrostatic potential

8.5 The electrochemical potential

8.6 Electrolytes and non‐electrolytes

8.7 Heterogeneous electron transfer

8.8 The future: supercatalysis by superexchange

References

Note

9 Constant potential rate theory – general formulation and electrocatalysis

9.1 Kinetics at electrochemical interfaces

9.2 Rate theory in the grand canonical ensemble

9.3 Adiabatic reactions

9.4 Non‐adiabatic reactions

9.5 Computational aspects

9.6 Conclusions

References

Part V:

10 Thermodynamically consistent free energy diagrams with the solvated jellium method

10.1 Computational studies of electrochemical systems – Recent advances and modern challenges

10.2 Thermodynamic consistency with a decoupled computational electrode model

10.3 Solvated jellium method (SJM)

10.4 Example: Mechanistic studies of the hydrogen evolution reaction (HER)

References

11 Generation of Computational Data Sets for Machine Learning Applied to Battery Materials

11.1 Introduction

11.2 Computational workflows for production of moderate‐fidelity data sets

11.3 High‐Fidelity data sets: Ab initio molecular dynamics simulations

11.4 Machine Learning

Acknowledgements

References

Index

End User License Agreement