The Electronic Structures and Energies of the Lowest Excited States of the Ns0, Ns+, Ns− and Ns-H Defects in Diamond

This work has been carried out within the framework of the EUROfusion Consortium, funded by the European Union via the Euratom Research and Training Programme (grant agreement No. 101052200—EUROfusion). Views and opinions expressed are however those of the author(s) only and do not necessarily reflect those of the European Union or the European Commission. Neither the European Union nor the European Commission can be held responsible for them. AP also acknowledges, with thanks, the financial support provided by “Strengthening of the capacity of doctoral studies at the University of Latvia within the framework of the new doctoral model”, No. 8.2.2.0/20/I/006, and Scientific Research Project for Students and Young Researchers, Nr. SJZ/2021/5 implemented at the Institute of Solid State Physics, University of Latvia.This paper reports the energies and charge and spin distributions of the mono-substituted N defects, N0s, N+s, N−s and Ns-H in diamonds from direct Δ-SCF calculations based on Gaussian orbitals within the B3LYP function. These predict that (i) Ns0, Ns+ and Ns− all absorb in the region of the strong optical absorption at 270 nm (4.59 eV) reported by Khan et al., with the individual contributions dependent on the experimental conditions; (ii) Ns-H, or some other impurity, is responsible for the weak optical peak at 360 nm (3.44 eV); and that Ns+ is the source of the 520 nm (2.38 eV) absorption. All excitations below the absorption edge of the diamond host are predicted to be excitonic, with substantial re-distributions of charge and spin. The present calculations support the suggestion by Jones et al. that Ns+ contributes to, and in the absence of Ns0 is responsible for, the 4.59 eV optical absorption in N-doped diamonds. The semi-conductivity of the N-doped diamond is predicted to rise from a spin-flip thermal excitation of a CN hybrid orbital of the donor band resulting from multiple in-elastic phonon scattering. Calculations of the self-trapped exciton in the vicinity of Ns0 indicate that it is essentially a local defect consisting of an N and four nn C atoms, and that beyond these the host lattice is essential a pristine diamond as predicted by Ferrari et al. from the calculated EPR hyperfine constants. © 2023 by the authors.--//-- This is an open access article Platonenko A., Mackrodt W.C., Dovesi R.; The Electronic Structures and Energies of the Lowest Excited States of the Ns0, Ns+, Ns− and Ns-H Defects in Diamond; (2023) Materials, 16 (5), art. no. 1979; DOI: 10.3390/ma16051979; https://www.scopus.com/inward/record.uri?eid=2-s2.0-85149871852&doi=10.3390%2fma16051979&partnerID=40&md5=b11fbcbf91ce1013d1a0e817573fd2fe published under the CC BY 4.0 licence.EUROfusion Consortium, funded by the European Union via the Euratom Research and Training Programme (grant agreement No. 101052200—EUROfusion); Latvijas Universitate 8.2.2.0/20/I/006, SJZ/2021/5; Scientific Research Project for Students and Young Researchers, Nr. SJZ/2021/5 implemented at the Institute of Solid State Physics, University of Latvia; the Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union's Horizon 2020 Framework Programme H2020-WIDESPREAD-01–2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART2

Ab initio study of ground and excited states ofNiO(100) monolayer

Ab initio periodic Hartree-Fock calculations are reported of ground and d --&gt; d excited states of an unsupported NiO(100) monolayer in the ferromagnetic, ferrimagnetic, antiferromagnetic and fully frustrated spin alignments as a function of the lattice constant. The ground state is found to be highly ionic and insulating with a minimum energy lattice constant of 4.0 Angstrom. The Ni(d(8)) configuration is [xz)(2)(xy)(2)(xy)(2)(z(2))(1) (x(2) - y(2))(1)], as found Previously for the bulk, despite the reduced dimensionality leading to a reduction in the number of nearest neighbours and difference in the ligand-field ordering. The valence band DOS resembles closely that of the bulk with a majority weight of O(p) states at the upper edge leading to a charge-transfer system. The Ni d states occur similar to 1 eV below the O(p) band and are dispersed over similar to 4.5 eV in three distinct sub-bands. The relative stability of the four spin alignments is antiferromagnetic &gt; ferrimagnetic &gt; ferromagnetic &gt; fully frustrated, with differences in energy of 10.779 meV, 10.017 meV and 1.675 meV respectively at 4.0 Angstrom. Values of -0.84 meV and -10.78 meV can be deduced for the direct spin-spin, Ed, and superexchange, E-se, interaction energies respectively, which compare with values of -1.5 meV and -7.0 meV found previously for the bulk at a lattice constant of 4.265 Angstrom. E-se is found to decrease rapidly to -3.66 meV at 4.5 Angstrom, unlike E-d which remains fairly constant. This reduction in E-se is attributed largely to the increase in the band gap of the monolayer compared with the bulk. For the ferromagnetic spin alignment at 4.0 Angstrom variationally converged solutions have been obtained for the one-electron d(xy) --&gt; d(z)2, d(xy) --&gt; d(x2-y2) and spin-forbidden d(x2-y2) --&gt; d(z2) excited states and the two-electron d(xy)/d(yz) --&gt; d(z2)/d(x2-y2) excited state with excitation energies of 1.16 eV, 1.09 eV, 1.84 eV and 1.79 eV respectively. These are close to values that have been deduced from optical and EEL spectra and high-level cluster calculations. Converged solutions for the d(xy) --&gt; d(z2) excited state in the ferromagnetic alignment have been obtained for the concentration range 1-4 excited states per x 2 unit cell and in the other spin alignments for complete excitation at lattice constants from 3.9 to 5.0 Angstrom. These show d(xy) --&gt; d(z2) excitations, and by implication other d --&gt; d excitations, to be highly local with an interaction energy of &lt; 0.1 eV per excitation at saturation, to be independent of the spin alignment and to increase slightly with lattice constant. The favourable arrangement of the nearest neighbour unpaired spins in the d(xy) --&gt; d(z2) excited state leads to values of E-d, the direct spin-spin coupling energy, which are an order of magnitude greater than the ground state values and appreciably in excess of the bulk value. E-se, on the other hand, remains approximately the same.The first ionized state is found to be essentially d(8)L, as it is in the bulk, with strong localization of the hole in a p(pi) orbital of a single O atom and retention of the local Ni moments. By direct analogy with the changes in the oxygen k-edge spectrum of LixNi1-xO the band gap in the NiO(100) monolayer is estimated to be similar to 5.3 eV from the gap between the hole band and the conduction band edge. The first electron addition state is found to be essentially d(9)[(d(z2))(2)]. The energy of the single charge-transfer excitonic state of a 2 x 2 unit cell is estimated to be to be similar to 5.6 eV, in close agreement with the band gap deduced from the DOS of the first ionized state.</p

Ab initio study of ground and excited states ofNiO(100) monolayer

Ab initio periodic Hartree-Fock calculations are reported of ground and d --&gt; d excited states of an unsupported NiO(100) monolayer in the ferromagnetic, ferrimagnetic, antiferromagnetic and fully frustrated spin alignments as a function of the lattice constant. The ground state is found to be highly ionic and insulating with a minimum energy lattice constant of 4.0 Angstrom. The Ni(d(8)) configuration is [xz)(2)(xy)(2)(xy)(2)(z(2))(1) (x(2) - y(2))(1)], as found Previously for the bulk, despite the reduced dimensionality leading to a reduction in the number of nearest neighbours and difference in the ligand-field ordering. The valence band DOS resembles closely that of the bulk with a majority weight of O(p) states at the upper edge leading to a charge-transfer system. The Ni d states occur similar to 1 eV below the O(p) band and are dispersed over similar to 4.5 eV in three distinct sub-bands. The relative stability of the four spin alignments is antiferromagnetic &gt; ferrimagnetic &gt; ferromagnetic &gt; fully frustrated, with differences in energy of 10.779 meV, 10.017 meV and 1.675 meV respectively at 4.0 Angstrom. Values of -0.84 meV and -10.78 meV can be deduced for the direct spin-spin, Ed, and superexchange, E-se, interaction energies respectively, which compare with values of -1.5 meV and -7.0 meV found previously for the bulk at a lattice constant of 4.265 Angstrom. E-se is found to decrease rapidly to -3.66 meV at 4.5 Angstrom, unlike E-d which remains fairly constant. This reduction in E-se is attributed largely to the increase in the band gap of the monolayer compared with the bulk. For the ferromagnetic spin alignment at 4.0 Angstrom variationally converged solutions have been obtained for the one-electron d(xy) --&gt; d(z)2, d(xy) --&gt; d(x2-y2) and spin-forbidden d(x2-y2) --&gt; d(z2) excited states and the two-electron d(xy)/d(yz) --&gt; d(z2)/d(x2-y2) excited state with excitation energies of 1.16 eV, 1.09 eV, 1.84 eV and 1.79 eV respectively. These are close to values that have been deduced from optical and EEL spectra and high-level cluster calculations. Converged solutions for the d(xy) --&gt; d(z2) excited state in the ferromagnetic alignment have been obtained for the concentration range 1-4 excited states per x 2 unit cell and in the other spin alignments for complete excitation at lattice constants from 3.9 to 5.0 Angstrom. These show d(xy) --&gt; d(z2) excitations, and by implication other d --&gt; d excitations, to be highly local with an interaction energy of &lt; 0.1 eV per excitation at saturation, to be independent of the spin alignment and to increase slightly with lattice constant. The favourable arrangement of the nearest neighbour unpaired spins in the d(xy) --&gt; d(z2) excited state leads to values of E-d, the direct spin-spin coupling energy, which are an order of magnitude greater than the ground state values and appreciably in excess of the bulk value. E-se, on the other hand, remains approximately the same.The first ionized state is found to be essentially d(8)L, as it is in the bulk, with strong localization of the hole in a p(pi) orbital of a single O atom and retention of the local Ni moments. By direct analogy with the changes in the oxygen k-edge spectrum of LixNi1-xO the band gap in the NiO(100) monolayer is estimated to be similar to 5.3 eV from the gap between the hole band and the conduction band edge. The first electron addition state is found to be essentially d(9)[(d(z2))(2)]. The energy of the single charge-transfer excitonic state of a 2 x 2 unit cell is estimated to be to be similar to 5.6 eV, in close agreement with the band gap deduced from the DOS of the first ionized state.</p

A theoretical study of magnetic phase transitions in ultra-thin films: Application to NiO

Phase diagrams and critical temperatures of projected onto fcc (1 0 0) layers, which is believed to be applicable to first-row transition metal oxides such as VO, MnO and NiO, are obtained from mean field theory and Monte Carlo simulations. Within the regime, Jse > 0, which includes MnO and NiO, both approaches predict bicritical behaviour of the AF2 and AF3 antiferromagnetic spin alignments for odd numbers of layers greater than one and monocritical behaviour for even numbers of layers, even when films are described by single values of Jd and Jse. The ferromagnetic alignment, on the other hand, exhibits monocritical behaviour for all thicknesses from the monolayer through to the bulk. For values of (x = Jd/Jse) which are close to those obtained from first principles calculations for NiO and also those derived from measured magnon spectra, estimates of the thickness dependence of the critical temperature from Monte Carlo simulations are similar to that derived from linear polarised X-ray absorption spectra of NiO(1 0 0) ultra-thin films grown epitaxially on MgO(1 0 0) [D. Alders, L.H. Tjeng, F.C. Voogt, T. Hibma, G.A. Sawatzky, J. Vogel, M. Sacchi, S. Iacobucci, Phys. Rev. B 57 (1998) 11623]

A study of the electronic, magnetic, structural and dynamic properties of low-dimensional NiO on MgO(100) surfaces

Recent developments in the growth of ultra-thin epitaxial layers of oxides and the fabrication of a diversity of nanostructures has led to current interest in, and much speculation about, the properties of low dimensional systems. In this paper we report recent calculations for low dimensional NiO on MgO(100) surfaces both from first principles electronic structure calculations and free energy calculations based on surface lattice dynamics. The results include surface structures and dynamics at a range of temperatures and electronic structures of ground, excited, ionised, d --&gt; d and charge-transfer excitonic states in different spin alignments.</p

A study of the electronic, magnetic, structural and dynamic properties of low-dimensional NiO on MgO(100) surfaces

Recent developments in the growth of ultra-thin epitaxial layers of oxides and the fabrication of a diversity of nanostructures has led to current interest in, and much speculation about, the properties of low dimensional systems. In this paper we report recent calculations for low dimensional NiO on MgO(100) surfaces both from first principles electronic structure calculations and free energy calculations based on surface lattice dynamics. The results include surface structures and dynamics at a range of temperatures and electronic structures of ground, excited, ionised, d --&gt; d and charge-transfer excitonic states in different spin alignments.</p