Exploring covalently bonded diamondoid particles with valence photoelectron spectroscopy

TL;DR

This study uses valence photoelectron spectroscopy and computational methods to analyze how covalent bonding affects the electronic structure of diamondoid particles in the gas phase.

Contribution

It provides new insights into the electronic effects of covalent bonds in diamondoid clusters, supported by experimental and theoretical analysis.

Findings

Bond type influences electronic structure significantly.

Doubly bonded particles' electronic structure is bond-dependent.

Superposition of orbitals governs singly bonded particles.

Abstract

We investigated the valence electronic structure of diamondoid particles in the gas phase, utilizing valence photoelectron spectroscopy. The samples were singly or doubly covalently bonded dimers or trimers of the lower diamondoids. Both the bond type and the combination of bonding partners are shown to affect the overall electronic structure. For singly bonded particles, we observe a small impact of the bond on the electronic structure, whereas for doubly bonded particles, the connecting bond determines the electronic structure of the highest occupied orbitals. In the singly bonded particles a superposition of the bonding partner orbitals determines the overall electronic structure. The experimental findings are supported by density functional theory computations at the M06-2X/cc-pVDZ level of theory.