Interstitial nitrogen atoms in diamond. A quantum mechanical investigation of its electronic and vibrational properties

Salustro, Simone; Pascale, Fabien; Mackrodt, W. C.; Ravoux, Corentin; Erba, Alessandro; Dovesi, Roberto

doi:10.1039/c8cp02484g

Cited by 10 publications

(5 citation statements)

References 61 publications

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“…Second, we used the ab initio periodic code CRYSTAL17, on grounds of computational cost, for hybrid density-functional-theory-Hartree-Fock calculations (B3LYP, HSE06) [54,55]. A number of doped-diamond supercell calculations using the CRYSTAL program have been reported previously [42,43,[56][57][58][59][60][61][62][63][64]. This code uses localised Gaussian basis sets to evaluate energies and associated electronic properties [65][66][67].…”

Section: Theoretical/computational Methodsmentioning

confidence: 99%

Hunting the elusive shallow n-type donor – An ab initio study of Li and N co-doped diamond

Conejeros

Othman

Croot

et al. 2021

Carbon

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We report calculated energetics (at the GGA, and at the B3LYP, HSE06 hybrid density functional levels of theory) and electronic properties (B3LYP, HSE06) of Li and N co-doped diamond containing LiNx clusters (x = 1-4). Defect energies and structural properties at the GGA and hybrid (B3LYP, HSE06) levels of theory are very similar. Our results for isolated Li and N dopants agree with previous work in that they are not suitable candidates for shallow n-type donors. Here, we investigate the effects of addition of N atoms as a co-dopant with Li, which vary with the Li:N ratio and whether Li is interstitial or substitutional.Reaction energies, geometries, bonding and densities of states (DOS) are examined. Nitrogen stabilises substitutional rather than interstitial lithium. Atom-projected DOS show that the chief contributions to the defect states are not from orbitals on the dopant atoms themselves but from states associated with neighbouring carbon atoms. Only the tetrahedral 1:4 cluster, LiCN4, with substitutional Li is likely to behave as a shallow donor. We propose a nonmolecular synthetic route for preparation of the LiCN4-doped material via prior generation of the N4V centre at temperatures at which Li is mobile but LiCN4 clusters are not.

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Section: Theoretical/computational Methodsmentioning

confidence: 99%

Hunting the elusive shallow n-type donor – An ab initio study of Li and N co-doped diamond

Conejeros

Othman

Croot

et al. 2021

Carbon

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“…In addition and for the purpose of exact comparison, the EPR constants of the single ICN and ICC interstitial defects (Fig. 2), whose electronic structures and IR spectra have been reported previously, 1,30 have also been included in this study. As a preliminary comment, we note that IR spectra are able to provide, at least, in principle, information on all six defects, whereas EPR can only be used to study open shell systems so that both INN and ININ are excluded.…”

Section: Discussionmentioning

confidence: 99%

“…This same approach has been used previously to investigate the structural and vibrational features of the three single interstitial defects, Ixy. 1,30 Here, we pay particular attention to the EPR spectra for ICIC, ICIN, ICC, and ICN and compare the computed data with experiment.…”

Section: Introductionmentioning

confidence: 99%

Interstitial defects in diamond: A quantum mechanical simulation of their EPR constants and vibrational spectra

Colasuonno

Gentile

Mackrodt

et al. 2020

The Journal of Chemical Physics

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The local geometry, electronic structure, and vibrational features of three vicinal double interstitial defects in diamond, ICIC, ICIN, and ININ, are investigated and compared with those of three "simple" ⟨100⟩ interstitial defects, ICC, ICN, and INN, previously reported by Salustro et al. [Phys. Chem. Chem. Phys. 20, 16615 (2018)], using a similar quantum mechanical approach based on the B3LYP functional constructed from Gaussian-type basis sets, within a supercell scheme, as implemented in the CRYSTAL code. For the first time, the Fermi contact term and hyperfine coupling tensor B of the four open shell structures, ICIC, ICIN, ICC, and ICN, are evaluated and compared with the available experimental EPR data. For the two double interstitial defects, the agreement with experiment is good, whereas that for the single interstitials is found to be very poor, for which a likely reason is the incorrect attribution of the EPR spectra to uncertain atomic details of the microstructure of the samples. The infrared spectra of the three double interstitial defects exhibit at least two peaks that can be used for their characterization.

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“…This strategy, based on the hypothesis of the local character of these isolated modes is at hand with a simple keyword, FRAG-MENT, and is quite effective. 130 It has been applied recently to the investigation of a set of defects in diamond [131][132][133] .…”

Section: The Fragment Strategymentioning

confidence: 99%

The CRYSTAL code, 1976–2020 and beyond, a long story

Dovesi

Pascale

Civalleri

et al. 2020

The Journal of Chemical Physics

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CRYSTAL is a periodic ab initio code that uses a Gaussian-type basis set to express crystalline orbitals (i.e. Bloch functions). The use of atom-centred basis functions allows treating 3D (crystals), 2D (slabs), 1D (polymers) as well as 0D (molecules) systems on the same grounds. In turn, all-electron calculations are inherently permitted along with pseudopotential strategies. A variety of density functionals is implemented, including global and range-separated hybrids of various nature and, as an extreme case, Hartree-Fock (HF). The cost for HF or hybrids is only about 3-5 times larger than when using the local density approximation (LDA) or the generalized gradient approximation (GGA). Symmetry is fully exploited at all steps of the calculation. Many tools are available to modify the structure as given in input and simplify the construction of complicated objects, such as slabs, nanotubes, molecules, clusters. Many tensorial properties can be evaluated by using a single input keyword: elastic, piezoelectric, photoelastic, dielectric, as well as first and second hyperpolarizabilies, etc. The calculation of infrared and Raman spectra is available, and the intensities are computed analytically. Automated tools are available for the generation of the relevant configurations of solid solutions and/or disordered systems. Three versions of the code exist, serial, parallel and massive-parallel. In the second one the most relevant matrices are duplicated on each core, whereas in the third one the Fock matrix is distributed for diagonalization. All the relevant vectors are dynamically allocated and deallocated after use, making the code very agile. CRYSTAL can be used efficiently on high performance computing machines up to thousands of cores.

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Interstitial nitrogen atoms in diamond. A quantum mechanical investigation of its electronic and vibrational properties

Cited by 10 publications

References 61 publications

Hunting the elusive shallow n-type donor – An ab initio study of Li and N co-doped diamond

Hunting the elusive shallow n-type donor – An ab initio study of Li and N co-doped diamond

Interstitial defects in diamond: A quantum mechanical simulation of their EPR constants and vibrational spectra

The CRYSTAL code, 1976–2020 and beyond, a long story

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