Electron correlation decides the stability of cubic versus hexagonal boron nitride

Halo, Migen; Pisani, Cesare; Maschio, Lorenzo; Casassa, Silvia; Schütz, Martin; Usvyat, Denis

doi:10.1103/physrevb.83.035117

Cited by 25 publications

(26 citation statements)

References 58 publications

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“…In the case of boron nitride, due to the fact that standard DFT calculations cannot accurately describe the van der Waals interactions between the boron nitride layers of the hexagonal phase (h-BN), only the cubic phase (c-BN) is considered as a competing phase for the subnitride. However, as demonstrated by a number of experimental and theoretical works [64][65][66][67][68][69], it is generally accepted that c-BN is thermodynamically stable over h-BN at zero pressure and zero temperature conditions, and is also found to be stable up to relatively high pressures and high temperatures.…”

Section: Resultsmentioning

confidence: 99%

Thermodynamic stability and properties of boron subnitrides from first principles

2017

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We use the first-principles approach to clarify the thermodynamic stability as a function of pressure and temperature of three different α-rhombohedral-boron-like boron subnitrides, with the compositions of B 6 N, B 13 N 2 , and B 38 N 6 , proposed in the literature. We find that, out of these subnitrides with the structural units of B 12 (N-N), B 12 (NBN), and [B 12 (N − N)] 0.33 [B 12 (NBN)] 0.67 , respectively, only B 38 N 6 , represented by [B 12 (N − N)] 0.33 [B 12 (NBN)] 0.67 , is thermodynamically stable. Beyond a pressure of about 7.5 GPa depending on the temperature, also B 38 N 6 becomes unstable, and decomposes into cubic boron nitride and α-tetragonalboron-like boron subnitride B 50 N 2 . The thermodynamic stability of boron subnitrides and relevant competing phases is determined by the Gibbs free energy, in which the contributions from the lattice vibrations and the configurational disorder are obtained within the quasiharmonic and the mean-field approximations, respectively. We calculate lattice parameters, elastic constants, phonon and electronic density of states, and demonstrate that [B 12 (N − N)] 0.33 [B 12 (NBN)] 0.67 is both mechanically and dynamically stable, and is an electrical semiconductor. The simulated x-ray powder-diffraction pattern as well as the calculated lattice parameters of [B 12 (N − N)] 0.33 [B 12 (NBN)] 0.67 are found to be in good agreement with those of the experimentally synthesized boron subnitrides reported in the literature, verifying that B 38 N 6 is the stable composition of α-rhombohedral-boron-like boron subnitride.

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Section: Resultsmentioning

confidence: 99%

Thermodynamic stability and properties of boron subnitrides from first principles

2017

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“…The performance on diverse properties other than cohesive energies will be of interest. One notable example is the relative stability of crystalline polymorphs, 49,55,121 which traditionally represent a tough challenge for quantum chemistry methods. Another quantity of interest, where the range-separated double hybrids can become particularly effective, is physisorption on surfaces or in porous crystals.…”

Section: Discussionmentioning

confidence: 99%

“…[34][35][36][37][38][39][40][41][42][43][44][45] The adaptation of the local MP2 method to periodic systems has been done in the last decade, 18,46,47 and over the years has been successfully applied to quite a rich variety of systems. [48][49][50][51][52][53][54][55][56][57][58][59][60] The paper is structured as follows. In Sec.…”

Section: Introductionmentioning

confidence: 99%

Range-separated double-hybrid density-functional theory applied to periodic systems

Sansone

Civalleri

Usvyat

et al. 2015

The Journal of Chemical Physics

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Articles you may be interested inBasis convergence of range-separated density-functional theory J. Chem. Phys. 142, 074107 (2015) Quantum chemistry methods exploiting density-functional approximations for short-range electronelectron interactions and second-order Møller-Plesset (MP2) perturbation theory for long-range electron-electron interactions have been implemented for periodic systems using Gaussian-type basis functions and the local correlation framework. The performance of these range-separated double hybrids has been benchmarked on a significant set of systems including rare-gas, molecular, ionic, and covalent crystals. The use of spin-component-scaled MP2 for the long-range part has been tested as well. The results show that the value of µ = 0.5 bohr −1 for the range-separation parameter usually used for molecular systems is also a reasonable choice for solids. Overall, these range-separated double hybrids provide a good accuracy for binding energies using basis sets of moderate sizes such as cc-pVDZ and aug-cc-pVDZ. C 2015 AIP Publishing LLC. [http://dx

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“…Since in practical applications of the periodic LMP2 method the basis sets of the size/quality of A3 or A are usually utilized, 71,110,[121][122][123][124] for such basis sets, the lack of the diffuse functions has to be compensated by expansion of the PAOdomains (see also discussion in Sec. IV C).…”

Section: B Orbital Basis Set Convergencementioning

confidence: 99%

Linear-scaling explicitly correlated treatment of solids: Periodic local MP2-F12 method

Usvyat

2013

The Journal of Chemical Physics

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Linear scaling explicitly correlated MP2-F12 and ONIOM methods for the long-range interactions of the nanoscale clusters in methanol aqueous solutions J. Chem. Phys. 138, 014106 (2013) Theory and implementation of the periodic local MP2-F12 method in the 3*A fixed-amplitude ansatz is presented. The method is formulated in the direct space, employing local representation for the occupied, virtual, and auxiliary orbitals in the form of Wannier functions (WFs), projected atomic orbitals (PAOs), and atom-centered Gaussian-type orbitals, respectively. Local approximations are introduced, restricting the list of the explicitly correlated pairs, as well as occupied, virtual, and auxiliary spaces in the strong orthogonality projector to the pair-specific domains on the basis of spatial proximity of respective orbitals. The 4-index two-electron integrals appearing in the formalism are approximated via the direct-space density fitting technique. In this procedure, the fitting orbital spaces are also restricted to local fit-domains surrounding the fitted densities. The formulation of the method and its implementation exploits the translational symmetry and the site-group symmetries of the WFs. Test calculations are performed on LiH crystal. The results show that the periodic LMP2-F12 method substantially accelerates basis set convergence of the total correlation energy, and even more so the correlation energy differences. The resulting energies are quite insensitive to the resolution-of-the-identity domain sizes and the quality of the auxiliary basis sets. The convergence with the orbital domain size is somewhat slower, but still acceptable. Moreover, inclusion of slightly more diffuse functions, than those usually used in the periodic calculations, improves the convergence of the LMP2-F12 correlation energy with respect to both the size of the PAO-domains and the quality of the orbital basis set. At the same time, the essentially diffuse atomic orbitals from standard molecular basis sets, commonly utilized in molecular MP2-F12 calculations, but problematic in the periodic context, are not necessary for LMP2-F12 treatment of crystals. © 2013 AIP Publishing LLC.

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Electron correlation decides the stability of cubic versus hexagonal boron nitride

Cited by 25 publications

References 58 publications

Thermodynamic stability and properties of boron subnitrides from first principles

Thermodynamic stability and properties of boron subnitrides from first principles

Range-separated double-hybrid density-functional theory applied to periodic systems

Linear-scaling explicitly correlated treatment of solids: Periodic local MP2-F12 method

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