Atomic-Scale Modelling of Electrochemical Systems

ISBN-13: 9781119605614 / Angielski / Twarda / 2021 / 368 str.

Marko Melander; Tomi Laurila; Kari Laasonen

Spis treści

Part I 11 Introduction to Atomic Scale Electrochemistry 3Marko M. Melander, Tomi Laurila, and Kari Laasonen1.1 Background 31.2 The thermodynamics of electrified interface 41.2.1 Electrode 61.2.2 Electrical double layer 71.2.3 Solvation sheets 81.2.4 Electrode potential 81.3 Chemical interactions between the electrode and redox species 121.4 Reaction kinetics at electrochemical interfaces 131.4.1 Outer and inner sphere reactions 131.4.2 Computational aspects 161.4.3 Challenges 171.5 Charge transport 181.6 Mass transport to the electrode 181.7 Summary 19References 20Part II 252 Retrospective and Prospective Views of Electrochemical Electron Transfer Processes: Theory and Computations 27Renat R. Nazmutdinov and Jens Ulstrup2.1 Introduction - interfacial molecular electrochemistry in recent retrospective 272.1.1 An electrochemical renaissance 272.1.2 A bioelectrochemical renaissance 272.2 Analytical theory of molecular electrochemical ET processes 282.2.1 A Reference to molecular ET processes in homogeneous solution 282.2.2 Brief discussion of contemporary computational approaches 302.2.3 Molecular electrochemical ET processes and general chemical rate theory 312.2.4 Some electrochemical ET systems at metal electrodes 352.2.4.1 Some outer sphere electrochemical ET processes 352.2.4.2 Dissociative ET: the electrochemical peroxodisulfate reduction 382.2.5 d-band, cation, and spin catalysis 392.2.6 New solvent environments in simple electrochemical ET processes - ionic liquids 402.2.7 Proton transfer, proton conductivity, and proton coupled electron transfer (PCET) 402.2.7.1 Some further notes on the nature of PT/PCET processes 442.2.7.2 The electrochemical hydrogen evolution reaction, and the Tafel plot on mercury 442.3 Ballistic and stochastic (Kramers-Zusman) chemical rate theory 452.4 Early and recent views on chemical and electrochemical long-range ET 502.5 Molecular-scale electrochemical science 532.5.1 Electrochemical in situ STM and AFM 532.5.2 Nanoscale mapping of novel electrochemical surfaces 542.5.2.1 Self-assembled molecular monolayers (SAMs) of functionalized thiol [192-194] 542.5.3 Electrochemical single-molecule ET and conductivity of complex molecules 562.5.4 Selected cases of in situ STM and STS of organic and inorganic redox molecules 582.5.4.1 The viologens 582.5.4.2 Transition metal complexes as single-molecule in operando STM targets 592.5.5 Other single-entity nanoscale electrochemistry 612.5.5.1 Electrochemistry in low-dimensional carbon confinement 612.5.5.2 Electrochemistry of nano- and molecular-scale metallic nanoparticles 622.5.6 Elements of nanoscale and single-molecule bioelectrochemistry 632.5.6.1 A single-molecule electrochemical metalloprotein target - P. aeruginosa azurin 632.5.6.2 Electrochemical SPMs of metalloenzymes, and some other "puzzles" 652.6 Computational approaches to electrochemical surfaces and processes revisited 672.6.1 Theoretical methodologies and microscopic structure of electrochemical interfaces 672.6.2 The electrochemical process revisited 682.7 Quantum and computational electrochemistry in retrospect and prospect 692.7.1 Prospective conceptual challenges in quantum and computational electrochemistry 702.7.2 Prospective interfacial electrochemical target phenomena 712.7.2.1 Some conceptual, theoretical, and experimental notions and challenges 712.7.2.2 Non-traditional electrode surfaces and single-entity structure and function 712.7.2.3 Semiconductor and semimetal electrodes 722.7.2.4 Metal deposition and dissolution processes 722.7.2.5 Chiral surfaces and ET processes of chiral molecules 722.7.2.6 ET reactions involving hot electrons (femto-electrochemistry) 732.8 A few concluding remarks 73Acknowledgement 74References 74Part III 933 Continuum Embedding Models for Electrolyte Solutions in First-Principles Simulations of Electrochemistry 95Oliviero Andreussi, Francesco Nattino, and Nicolas Georg Hörmann3.1 Introduction to continuum models for electrochemistry 953.2 Continuum models of liquid solutions 973.2.1 Continuum interfaces 983.2.2 Beyond local interfaces 1033.2.3 Electrostatic interaction: polarizable dielectric embedding 1053.2.4 Beyond electrostatic interactions 1073.3 Continuum diffuse-layer models 1093.3.1 Continuum models of electrolytes 1093.3.2 Helmholtz double-layer model 1103.3.3 Poisson-Boltzmann model 1113.3.4 Size-modified Poisson-Boltzmann model 1133.3.5 Stern layer and additional interactions 1143.3.6 Performance of the diffuse-layer models 1143.4 Grand canonical simulations of electrochemical systems 1183.4.1 Thermodynamics of interfaces 1193.4.2 Ab-initio based thermodynamics of electrochemical interfaces 1213.4.3 Grand canonical simulations and the CHE approximation 1233.5 Selected applications 126Acknowledgments 129References 1294 Joint and grand-canonical density-functional theory 139Ravishankar Sundararaman and Tomás A. Arias4.1 Introduction 1394.2 JDFT variational theorem and framework 1424.2.1 Variational principle and underlying theorem 1424.2.2 Separation of effects and regrouping of terms 1464.2.3 Practical functionals and universal form for coupling 1474.3 Classical DFT with atomic-scale structure 1484.3.1 Ideal gas functionals with molecular geometry 1494.3.1.1 Effective ideal gas potentials 1494.3.1.2 Integration over molecular orientations 1504.3.1.3 Auxiliary fields 1514.3.2 Minimal excess functionals for molecular fluids 1524.4 Continuum solvation models from JDFT 1574.4.1 JDFT linear response: nonlocal 'SaLSA' solvation 1584.4.2 JDFT local limit: nonlinear continuum solvation 1604.4.3 Hybrid semi-empirical approaches: 'CANDLE' solvation 1634.5 Grand-canonical DFT 1644.6 Conclusions 168References 1695 Ab initio modeling of electrochemical interfaces and determination of electrode potentials 173Jia-Bo Le, Xiao-Hui Yang, Yong-Bing Zhuang, Feng Wang, and Jun Cheng5.1 Introduction 1735.2 Theoretical background of electrochemistry 1755.2.1 Definition of electrode potential 1755.2.2 Absolute potential energy of SHE 1785.3 Short survey of computational methods for modeling electrochemical interfaces 1795.4 Ab initio determination of electrode potentials of electrochemical interfaces 1805.4.1 Work function based methods 1805.4.1.1 Vacuum reference 1805.4.1.2 Vacuum reference in two steps 1815.4.2 Reference electrode based methods 1835.4.2.1 Computational standard hydrogen electrode 1835.4.2.2 Computational standard hydrogen electrode in two steps 1855.4.2.3 Computational Ag/AgCl reference electrode 1875.5 Computation of potentials of zero charge 1875.6 Summary 190Acknowledgement 191References 1916 Molecular Dynamics of the Electrochemical Interface and the Double Layer 201Axel Groß6.1 Introduction 2016.2 Continuum description of the electric double layer 2026.3 Equilibrium coverage of metal electrodes 2046.4 First-principles simulations of electrochemical interfaces and electric double layers 2096.5 Electric double layers at battery electrodes 2136.6 Conclusions 216Acknowledgement 216References 2177 Atomic-Scale Modelling of Electrochemical Interfaces through Constant Fermi Level Molecular Dynamics 221Assil Bouzid and Alfredo Pasquarello7.1 Introduction 2217.2 Method 2227.3 CFL-MD in aqueous solution: Determination of redox levels 2237.4 CFL-MD at metal-water interface: The case of the Volmer reaction 2287.5 Referencing the bias potential to the SHE 2307.6 Macroscopic properties at the metal-water interface 2327.7 Atomic-scale processes at the metal-water interface 2367.8 Conclusion 238Acknowledgements 238References 239Part IV 2418 From electrons to electrode kinetics: A tutorial review 243Stephen Fletcher8.1 Global electro-neutrality 2438.2 The electrochemical reference state 2438.3 The chemical potential 2468.4 The electrostatic potential 2468.5 The electrochemical potential 2468.5.1 The molar electrochemical potential 2488.5.2 The electrochemical potential of a single electron 2488.5.3 The Nernst equation 2488.5.4 Fermi-Dirac distribution function 2508.5.5 The molar electrochemical potential of an electron 2518.5.6 Parsing the electrochemical potential. (I) Metal in a vacuum 2518.5.7 The Volta potential difference 2528.5.8 Scanning Kelvin Probe Microscopy 2538.5.9 The membrane potential 2548.5.10 The electrochemical potential of a single proton 2548.5.11 The proton motive force 2558.5.12 The standard hydrogen half-cell 2568.5.13 The hydrated electron 2578.5.14 The hydrogen atom H* 2588.5.15 Parsing the electrochemical potential. (II) The co-sphere 2588.5.16 Electron transfer (general introduction) 2598.5.17 Johnson-Nyquist noise 2608.5.18 The Molar Gibbs reorganization energy 2608.5.19 The reaction co-ordinate 2618.5.20 The vertical energy gap 2618.5.21 Permittivity of solutions 2638.6 Electrolytes and non-electrolytes 2638.6.1 Equivalent circuit of a non-electrolyte solution 2658.6.2 Equivalent circuit of an electrolyte solution 2658.6.3 Probability of an electron jump 2668.6.4 The Klopman-Salem equation 2678.6.5 Electrode kinetics 2688.6.6 Homogeneous kinetics, first order 2698.6.7 Homogeneous kinetics, second order 2698.6.8 Homogeneous versus heterogeneous kinetics 2708.6.9 Tunneling layer approximation 2718.6.10 The back of the envelope 2728.6.11 The total rate constant of an electron transfer process 2738.7 Heterogeneous electron transfer 2758.7.1 Tafel slopes for multi-step reactions 2788.8 The future: supercatalysis by superexchange 280References 2829 Constant potential rate theory - general formulation and electrocatalysis 287Marko M. Melander9.1 Kinetics at electrochemical interfaces 2879.2 Rate theory in the grand canonical ensemble 2889.3 Adiabatic reactions 2899.3.1 Classical nuclei 2899.3.2 Fixed potential empirical valence bond theory 2909.3.3 Nuclear tunneling 2919.4 Non-adiabatic reactions 2929.4.1 Non-adiabatic reactions in electrochemistry 2929.4.2 Rate of ET and CPET reactions 2939.5 Computational aspects 2959.6 Conclusions 296References 297Part V 30110 Thermodynamically consistent free energy diagrams with the solvated jellium method 303Georg Kastlunger, Per Lindgren, and Andrew A. Peterson10.1 Computational studies of electrochemical systems - Recent advances and modern challenges 30310.2 Thermodynamic consistency with a decoupled computational electrode model 30510.3 Solvated jellium method (SJM) 30810.3.1 Introduction 30810.3.2 Electrostatic potential profiles and charge localization 30910.3.3 Workflow of potential equilibration 31310.3.4 Shape of the jellium background charge 31910.4 Example: Mechanistic studies of the hydrogen evolution reaction (HER) 31910.4.1 Potential dependence of the elementary steps of HER 32010.4.2 Charge transfer along reaction trajectories 32310.4.3 Thermodynamically consistent free energy diagrams from first principles 323References 32611 Generation of Computational Data Sets for Machine Learning Applied to Battery Materials 329Arghya Bhowmik, Felix Tim Bölle, Ivano E. Castelli, Jin Hyun Chang, Juan Maria García Lastra, Nicolai Rask Mathiesen, Alexander Sougaard Tygesen, and Tejs Vegge11.1 Introduction 32911.2 Computational workflows for production of moderate-fidelity data sets 33011.2.1 Ionic diffusion: NEB calculations 33311.2.1.1 Symmetric NEB 33311.2.1.2 Choice of functionals for NEB 33511.2.2 Disordered materials: Cluster Expansion 33711.3 High-Fidelity data sets: Ab initio molecular dynamics simulations 34011.4 Machine Learning 343Acknowledgements 346References 346Index 355

O autorze

Marko M. Melander, PhD, is a researcher and adjunct professor in physical (electro)chemistry at the University of Jyväskylä in the Department of Chemistry. His work focuses on the development of theory and computational methodologies for studying (proton-coupled) electron transfer thermodynamics and kinetics at electrochemical interfaces.Tomi T. Laurila, PhD is an Associate Professor in the Department of Electrical Engineering and Automation and Department of Chemistry and Materials Science at Aalto University in Finland where he leads the group of Microsystems Technology. The research focus of his group is on electrochemical properties of various carbon nanomaterials, computational materials science and applications of carbon nanomaterials in different sensing devices.Kari Laasonen, PhD, is a Professor in the Department of Chemistry and Materials Science at Aalto University, Finland. He has been working on computational molecular modeling since the early 1990's. He has a strong background in ab initio molecular dynamics and modelling of aqueous systems, and his group started to model electrochemical reactions in early 2010, focusing on hydrogen and oxygen evolution reactions on different catalysts.