The electronic states of the neutral vacancy in diamond: a quantum mechanical approach

Zelferino, Alessandro; Salustro, Simone; Baima, Jacopo; Lacivita, Valentina; Orlando, Roberto; Dovesi, Roberto

doi:10.1007/s00214-016-1813-0

Cited by 30 publications

(34 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The corresponding cluster has been denominated specifying that one C atom is missing or has been added: then, for instance, C 35−1 H 36 and C 35+1 H 36 indicate, respectively, a cluster with a vacancy or an interstitial defect. Cluster properties have been compared with those of supercells (S 128 ) containing, before the defect creation, 128 carbon atoms [39][40][41].…”

Section: Clustermentioning

confidence: 99%

“…This combination has shown to provide accurate description of the properties of both regular and defective diamond. [39][40][41] In the cluster calculations, terminal hydrogen atoms have been described at the STO-3G [48] level. To increase the variational freedom in the vacancy region, the same C basis set has been placed at the vacancy site (see the GHOSTS option in the CRYSTAL manual [44] Fig.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Cluster SCF equations have been solved at the Γ point of the reciprocal lattice while 4 k-points in the irreducible part of the Brillouin zone (corresponding to a "shrinking factor" of 4) had been selected for the reference S 128 supercell calculations, see Refs. [39][40][41] for details. In geometry optimization two different procedure have been followed: in the former only the H atoms have been kept fixed at their initial positions and all C atoms have been fully relaxed (we refer to these clusters as FULL); in the latter approach only C atoms in the internal shells of the clusters have been relaxed, that means all C atoms not linked to H but also not at the border of the cluster (we refer to these clusters as FRAGMENT).…”

Section: Computational Detailsmentioning

confidence: 99%

“…Pure diamond is characterized by a single Raman peak at 1332 cm −1 ; the same peak, computed within the periodic approach is at 1318 cm −1 , see Refs. [39][40][41] for a detailed discussion. However, when a cluster approach is adopted, spurious peaks due to border effects are expected.…”

Section: Non Defective Diamondmentioning

confidence: 99%

“…Defect formation energies, atomic relaxations, band structure of the defect, relative energies of different spin states and Raman spectra are investigated as a function of the cluster size, and are compared directly with the results of wellconverged supercells calculations. [39][40][41]. This latter method involves a periodic array of unit cells of the host crystal containing the defect at the centre.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Comparison between cluster and supercell approaches: the case of defects in diamond

et al. 2017

Self Cite

View full text Add to dashboard Cite

The results produced by the cluster and the supercell approaches, when applied to the study of the vacancy and 100 split self-interstitial defects in diamond, are critically compared. The same computer code, CRYSTAL, basis set and DFT functional (the hybrid B3LYP) are used. Clusters of increasing size (from 35 to 969 C atoms) are considered, and the results compared to those from a supercell containg 128±1 atoms, for which the interaction between defects in different cells can be considered negligible. It is shown that geometry and energy data (atomic relaxation, defect formation energy, relative energy between different spin states) show a very local nature and then converge rapidly with the cluster size. Other properties, frequently used for the characterization of the defects using relatively small clusters (band gaps, impurity energy levels in the gap, Raman spectra) converge slowly, and also at the limit of the very large clusters here considered, still differ from the periodic counterpart.

show abstract

Section: Clustermentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Section: Non Defective Diamondmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Comparison between cluster and supercell approaches: the case of defects in diamond

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

Looking for $$sp^2$$ s p 2 carbon atoms in diamond: a quantum mechanical study of interacting vacancies

et al. 2018

Self Cite

View full text Add to dashboard Cite

This paper reports the calculated relaxed lattice configurations and corresponding electronic and magnetic structures, and Raman frequencies of two divacancies in diamond, V2 and VC=CV, in which the vacancies are first and third neighbours respectively. The calculations are formulated within a supercell approach to local defects in crystalline solids, here 64-and 128-atoms unit cells and based largely on the B3LYP one-electron approximation constructed from an all-electron Gaussian basis set. Three important findings are first, that, of the four possible spin states, Sz=0, 1, 2, 3, the singlet is predicted to be lowest in energy for both divacancies; second, that the singlet state of V2 is ∼1.7 eV lower in energy than that in VC=CV; and third, that the Raman peak at 1628 cm −1 in defective diamond can be ascribed to the presence of a C=C double bond, as in the singlet state of VC=CV.

show abstract

Hydrogen, boron and nitrogen atoms in diamond: a quantum mechanical vibrational analysis

et al. 2018

Self Cite

View full text Add to dashboard Cite

The structural, electronic and vibrational properties of two common defects in diamond, CHN and CHB, describing the case in which a carbon C 1 atom is substituted by a nitrogen atom, or by a boron atom, breaking a C 1-C 2 bond, followed by the saturation of the dangling bond of C 2 by a hydrogen atom, are investigated at the quantum mechanical level, by using a periodic supercell approach, hybrid DFT functionals and a local Gaussian-type basis set as implemented in the CRYSTAL code. The effect of concentration of the defects has been explored, by considering two supercells containing 64 and 216 atoms (S 64 and S 216). Formation and hydrogenation energies, geometries, Mulliken charges and the band structure of both defects are reported. The vibrational features of the defects have been investigated, by generating the IR and Raman spectra, and by analyzing graphically and through the isotopic substitution (H → D, 11 B → 10 B and 14 N → 15 N) the nature of the most relevant modes related to the defects. The computed C-H stretching mode of CHN, once corrected for anharmonicity (3408 cm −1), falls to wavenumbers very close to the experimental peak observed at 3394 cm −1 , which can then be reasonably attributed to this specific defect. The present manuscript is included in a special volume in honor and memory of János Ángyán. Although he did not study in particular the kind of defects discussed in the present manuscript, the many methodological contributions he introduced in computational science have inspired many of the tools we have been using here. One of the present authors, RD, in particular, is grateful to János for the illuminating discussions they had in Paris, Nancy and Torino.

show abstract

The electronic states of the neutral vacancy in diamond: a quantum mechanical approach

Cited by 30 publications

References 45 publications

Comparison between cluster and supercell approaches: the case of defects in diamond

Comparison between cluster and supercell approaches: the case of defects in diamond

Looking for $$sp^2$$ s p 2 carbon atoms in diamond: a quantum mechanical study of interacting vacancies

Hydrogen, boron and nitrogen atoms in diamond: a quantum mechanical vibrational analysis

Contact Info

Product

Resources

About