Structural and Bonding Issues in Clusters and Nano-clusters - Gold Clusters, Colloids and Nanoparticles - page 2

Contents
1 Introduction ................................................................................... 3
2 Single Crystal X-Ray Structural Determinations ............................................ 4
3 Theoretical Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.1 Brief Historical Introduction to Theoretical Models . . . .................................. 11

3.2 Bonding in Simple Gold Clusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

3.3 Introduction of Interstitial Atoms . . . . . . . .................................................. 18

3.4 Bonding in Condensed and Fused Clusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

3.5 Introduction of Interstitial Atoms . . . . . . . .................................................. 34

3.6 Bonding Interrelationships Between Organothiolato- and Gold Phosphine Clusters . . . 35

3.7 Construction of Organothiolato-Clusters from Phosphine Cluster Building Blocks .... 38

3.8 Inherent Structure Rule and the Superatom Model . . . . . . . . . . . . .......................... 49

3.9 52

3.10 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Spherical and Close-Packed Arrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

56
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

Abbreviations

ANP Gold nano-particle
Ar Aryl
ccp Cubic close packed
ccs Collision cross section
DFT Density functional theory
dmf Dimethylformamide
dppe Bis(diphenylphosphino)ethane
dppm Bis(diphenylphosphino)methane
dppp Bis(diphenylphosphino)propane
Et Ethyl
hcp Hexagonal close packed
HOMO Highest occupied molecular orbital
HRTEM High resolution transmission electron microscopy
IM-MS Combined ion mobility mass spectrometry

IMS Ion mobility mass spectrometry

i -Pr Isopropyl

LUMO Lowest unoccupied molecular orbital

Me Methyl

Mes Mesityl, 2,4,6-trimethylphenyl (not methanesulfonyl)

MS Mass spectrometry

octyl n -Octyl

Pc Phthalocyanine

pec Polyhedral skeletal electron pair count

Ph Phenyl

Pr Propyl

sec Skeletal electron count