### Abstract

Diamondoids are small diamond nanoparticles (NPs) that are built up from diamond cages. Unlike usual semiconductor NPs, their atomic structure is exactly known, thus they are ideal test-beds for benchmarking quantum chemical calculations. Their usage in spintronics and bioimaging applications requires a detailed knowledge of their electronic structure and optical properties. In this paper, we apply density functional theory (DFT) based methods to understand the electronic and optical properties of a few selected pure and modified diamondoids for which accurate experimental data exist. In particular, we use many-body perturbation theory methods, in the G_{0}W_{0} and G_{0}W_{0}+BSE approximations, and time-dependent DFT in the adiabatic local density approximation. We find large quasiparticle gap corrections that can exceed thrice the DFT gap. The electron-hole binding energy can be as large as 4 eV but it is considerably smaller than the GW corrections and thus G_{0}W_{0}+BSE optical gaps are about 50% larger than the Kohn-Sham (KS) DFT gaps. We find significant differences between KS time-dependent DFT and GW+BSE optical spectra on the selected diamondoids. The calculated G_{0}W_{0} quasiparticle levels agree well with the corresponding experimental vertical ionization energies. We show that nuclei dynamics in the ionization process can be significant and its contribution may reach about 0.5 eV in the adiabatic ionization energies.

Original language | English |
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Article number | 064308 |

Journal | Journal of Chemical Physics |

Volume | 141 |

Issue number | 6 |

DOIs | |

Publication status | Published - aug. 14 2014 |

### ASJC Scopus subject areas

- Physics and Astronomy(all)
- Physical and Theoretical Chemistry

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## Cite this

*Journal of Chemical Physics*,

*141*(6), [064308]. https://doi.org/10.1063/1.4891930