Cover Page The following handle holds various files of this Leiden University dissertation: http://hdl.handle.net/1887/76855

Cover Page

The following handle holds various files of this Leiden University dissertation:

http://hdl.handle.net/1887/76855

Author: Nour Ghassemi, E.

Hydrogen Dissociation

on

Metal Surfaces

A Semi-empirical Approach

PROEFSCHRIFT

ter verkrijging van

de graad van Doctor aan de Universiteit Leiden, op gezag van Rector Magnificus prof. mr. C.J.J.M. Stolker,

volgens besluit van het College voor Promoties te verdedigen op donderdag 19 september 2019

klokke 11:15 uur

door

ii

Promotor: Prof. dr. G. J. Kroes

Co-promotor: Dr. M. F. Somers

Promotiecommissie: Prof. dr. H. S. Overkleeft (voorzitter) Prof. dr. M. T. M. Koper (secretaris)

Overige commissieleden: Prof. dr. A. Groß (Universität Ulm, Duitsland) Prof. dr. G. C. Groenenboom (Radboud Universiteit Nijmegen)

Dr. C. Díaz (Universidad Autónoma de Madrid, Spanje)

Dr. I. M. N. Groot

European Research Council

The work in this thesis was supported by the ERC Advanced grant 338580.

ISBN: 978-94-028-1638-9

iii

Typeset with LA_TEX.

Cover design and printed by: IPSKAMP.

v

Contents

Contents vii

1 Introduction 1

1.1 Reactions of molecules on surfaces . . . 3

1.2 Scattering of molecules from surfaces . . . 7

1.3 Aim of this thesis . . . 14

1.4 Main results. . . 15

1.5 Outlook . . . 18

2 Theoretical Background 29 2.1 Modelling the molecule surface interaction . . . 31

2.2 Density functional theory . . . 33

2.3 Density functional theory for periodic systems. . . 39

2.4 Construction of potential energy surfaces . . . 41

2.5 Molecular dynamics . . . 44

3 Chemically Accurate Simulation of Dissociative Chemisorp-tion of D2 on Pt(111) 59 3.1 Introduction. . . 61

3.2 Method . . . 63

3.3 Results and discussion . . . 68

3.4 Conclusions and outlook . . . 77

4 Test of the Transferability of the Specific Reaction Para-meter Functional for H2 + Cu(111) to D2 + Ag(111) 85 4.1 Introduction. . . 87

4.2 Method . . . 92

viii CONTENTS

4.4 Conclusions . . . 119

5 Transferability of the Specific Reaction Parameter Dens-ity Functional for H2 + Pt(111) to H2 + Pt(211) 131 5.1 Introduction. . . 133

5.2 Theoretical methodology. . . 138

5.3 Results and discussion . . . 151

5.4 Conclusion . . . 169

6 Assessment of Two Problems of Specific Reaction Para-meter Density Functional Theory : Sticking and Diffrac-tion of H2 on Pt(111) 179 6.1 Introduction. . . 182

6.2 Experiments and beam parameters used to simulate the ex-periments . . . 185

6.3 Method . . . 194

6.4 Results and discussion . . . 200