Electronic and optical properties of pure and modified diamondoids studied by many-body perturbation theory and time-dependent density functional theory
| Autor: | Maurizia Palummo, Márton Vörös, Adam Gali, Tamás Demján |
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| Rok vydání: | 2014 |
| Předmět: |
Chemistry
General Physics and Astronomy Electronic structure Time-dependent density functional theory Diamondoid Settore FIS/03 - Fisica della Materia Ionization Physics::Atomic and Molecular Clusters Quasiparticle Density functional theory Physical and Theoretical Chemistry Perturbation theory Local-density approximation Atomic physics |
| Zdroj: | The Journal of chemical physics. 141(6) |
| ISSN: | 1089-7690 |
| Popis: | 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 G0W0 and G0W0+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 G0W0+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 G0W0 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. |
| Databáze: | OpenAIRE |
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