Atomic-Scale Modelling of Electrochemical Systems

Marko M. Melander, PhD, is a researcher and adjunct professor in physical (electro)chemistry at the University of Jyvskyl 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 1990s. 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.

Part I 1 1 Introduction to Atomic Scale Electrochemistry 3 Marko M. Melander, Tomi Laurila, and Kari Laasonen 1.1 Background 3 1.2 The thermodynamics of electrified interface 4 1.2.1 Electrode 6 1.2.2 Electrical double layer 7 1.2.3 Solvation sheets 8 1.2.4 Electrode potential 8 1.3 Chemical interactions between the electrode and redox species 12 1.4 Reaction kinetics at electrochemical interfaces 13 1.4.1 Outer and inner sphere reactions 13 1.4.2 Computational aspects 16 1.4.3 Challenges 17 1.5 Charge transport 18 1.6 Mass transport to the electrode 18 1.7 Summary 19 References 20 Part II 25 2 Retrospective and Prospective Views of Electrochemical Electron Transfer Processes: Theory and Computations 27 Renat R. Nazmutdinov and Jens Ulstrup 2.1 Introduction interfacial molecular electrochemistry in recent retrospective 27 2.1.1 An electrochemical renaissance 27 2.1.2 A bioelectrochemical renaissance 27 2.2 Analytical theory of molecular electrochemical ET processes 28 2.2.1 A Reference to molecular ET processes in homogeneous solution 28 2.2.2 Brief discussion of contemporary computational approaches 30 2.2.3 Molecular electrochemical ET processes and general chemical rate theory 31 2.2.4 Some electrochemical ET systems at metal electrodes 35 2.2.4.1 Some outer sphere electrochemical ET processes 35 2.2.4.2 Dissociative ET: the electrochemical peroxodisulfate reduction 38 2.2.5 d-band, cation, and spin catalysis 39 2.2.6 New solvent environments in simple electrochemical ET processes ionic liquids 40 2.2.7 Proton transfer, proton conductivity, and proton coupled electron transfer (PCET) 40 2.2.7.1 Some further notes on the nature of PT/PCET processes 44 2.2.7.2 The electrochemical hydrogen evolution reaction, and the Tafel plot on mercury 44 2.3 Ballistic and stochastic (Kramers-Zusman) chemical rate theory 45 2.4 Early and recent views on chemical and electrochemical long-range ET 50 2.5 Molecular-scale electrochemical science 53 2.5.1 Electrochemical in situ STM and AFM 53 2.5.2 Nanoscale mapping of novel electrochemical surfaces 54 2.5.2.1 Self-assembled molecular monolayers (SAMs) of functionalized thiol [192194] 54 2.5.3 Electrochemical single-molecule ET and conductivity of complex molecules 56 2.5.4 Selected cases of in situ STM and STS of organic and inorganic redox molecules 58 2.5.4.1 The viologens 58 2.5.4.2 Transition metal complexes as single-molecule in operando STM targets 59 2.5.5 Other single-entity nanoscale electrochemistry 61 2.5.5.1 Electrochemistry in low-dimensional carbon confinement 61 2.5.5.2 Electrochemistry of nano- and molecular-scale metallic nanoparticles 62 2.5.6 Elements of nanoscale and single-molecule bioelectrochemistry 63 2.5.6.1 A single-molecule electrochemical metalloprotein target P. aeruginosa azurin 63 2.5.6.2 Electrochemical SPMs of metalloenzymes, and some other puzzles 65 2.6 Computational approaches to electrochemical surfaces and processes revisited 67 2.6.1 Theoretical methodologies and microscopic structure of electrochemical interfaces 67 2.6.2 The electrochemical process revisited 68 2.7 Quantum and computational electrochemistry in retrospect and prospect 69 2.7.1 Prospective conceptual challenges in quantum and computational electrochemistry 70 2.7.2 Prospective interfacial electrochemical target phenomena 71 2.7.2.1 Some conceptual, theoretical, and experimental notions and challenges 71 2.7.2.2 Non-traditional electrode surfaces and single-entity structure and function 71 2.7.2.3 Semiconductor and semimetal electrodes 72 2.7.2.4 Metal deposition and dissolution processes 72 2.7.2.5 Chiral surfaces and ET processes of chiral molecules 72 2.7.2.6 ET reactions involving hot electrons (femto-electrochemistry) 73 2.8 A few concluding remarks 73 Acknowledgement 74 References 74 Part III 93 3 Continuum Embedding Models for Elect