Approaching the theoretical limit in periodic local MP2 calculations with atomic-orbital basis sets: The case of LiH

Usvyat, Denis; Civalleri, Bartolomeo; Maschio, Lorenzo; Dovesi, Roberto; Pisani, Cesare; Schütz, Martin

doi:10.1063/1.3595514

Cited by 55 publications

(75 citation statements)

References 36 publications

(62 reference statements)

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“…Our MP2 and MP2-F12 (using a STG) results converge to the same complete basis set limit results obtained using local MP2 (CRYSCOR, from Ref. 13), the hierarchical method (from Ref. [8]) and the incremental scheme (from Ref.…”

Section: Discussionmentioning

confidence: 68%

“…Nowhere is this more true than in the solid state, where application of high-level quantum chemistry methods are only beginning to emerge in a recently growing field [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. The reason for this slow uptake is the computational cost of these methods, which generally scale as a high power of the system size, compared to the lower mean-field scaling of DFT.…”

Section: Introductionmentioning

confidence: 99%

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Explicitly correlated plane waves: Accelerating convergence in periodic wavefunction expansions

Grüneis

Shepherd

Alavi

et al. 2013

The Journal of Chemical Physics

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We present an investigation into the use of an explicitly correlated plane wave basis for periodic wavefunction expansions at the level of second-order Møller-Plesset perturbation theory (MP2). The convergence of the electronic correlation energy with respect to the one-electron basis set is investigated and compared to conventional MP2 theory in a finite homogeneous electron gas model. In addition to the widely used Slater-type geminal correlation factor, we also derive and investigate a novel correlation factor that we term Yukawa-Coulomb. The Yukawa-Coulomb correlation factor is motivated by analytic results for two electrons in a box and allows for a further improved convergence of the correlation energies with respect to the employed basis set. We find the combination of the infinitely delocalized plane waves and local short-ranged geminals provides a complementary, and rapidly convergent basis for the description of periodic wavefunctions. We hope that this approach will expand the scope of discrete wavefunction expansions in periodic systems.

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Section: Discussionmentioning

confidence: 68%

Section: Introductionmentioning

confidence: 99%

Explicitly correlated plane waves: Accelerating convergence in periodic wavefunction expansions

Grüneis

Shepherd

Alavi

et al. 2013

The Journal of Chemical Physics

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“…107,108 As for the C calculations, we adopted a homogeneous 8 × 8 × 8 k-point sampling of the reciprocal space, and integral-screening tolerances set to 10 −8 , 10 −8 , 10 −8 , 10 −20 , 10 −50 . For the meaning of these thresholds, we address the user to the C14 user's manual; 109 here, we just point out that, as in our previous works, 93,95 we tightened the thresholds for the exchange integrals (last two numbers) with respect to defaults.…”

Section: B Parameters Of the Calculationsmentioning

confidence: 99%

“…85 The LiH crystal, being the simplest 3D crystal, has been the subject of much attention recently, 19,[86][87][88][89][90][91][92] and convergence of the total MP2 energy with basis set was carefully investigated by some of us. 93 The three molecular crystals have been chosen in order to evaluate different natures of interactions which contribute to the total cohesion energy. This includes dispersive and electrostatic quadrupole-quadrupole interactions 94 in CO 2 crystal and hydrogen bonds in NH 3 crystal.…”

Section: Computational Details a Test Systemsmentioning

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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“…In order to compute a potential-energy surface for the He-MgO(100) system we employ periodic local Møller-Plesset perturbation theory of second order (periodic LMP2) [20,24,25], which is the highest-order periodic ab initio approach presently affordable for such a system. A reasonably large atom centered Gaussian basis set of triple-zeta quality for Mg and oxygen, and quadruple-zeta quality for He, augmented with diffuse orbitals (for oxygen and He atoms) was used (details of the basis set can be found in Ref.…”

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confidence: 99%

Approaching an exact treatment of electronic correlations at solid surfaces: The binding energy of the lowest bound state of helium adsorbed on MgO(100)

et al. 2014

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In this work we employ ab initio electronic structure theory at a very high level to resolve a long standing experimental controversy; the interaction between helium and the MgO (100) surface has been studied extensively by other groups, employing diverse experimental approaches. Nevertheless, the binding energy of the lowest bound state is still unclear: the existence of a state at around −5.5 meV is well established but a state at −10 meV has also been reported. The MgO (100)-He system captures the fundamental physics involved in many adsorption problems; the weak binding is governed by long-range electronic correlation for which a fully predictive theory applicable to the solid state has been elusive. The above-mentioned experimental controversy can now be resolved on the basis of the calculations presented in this work. We performed three-dimensional vibrational dynamics calculations on a highly accurate potential-energy surface. The latter was constructed using a method which systematically approaches the exact limit in its treatment of electronic correlation. The outcome is clear: our calculations do not support the existence of a bound state around −10 meV. The interaction between molecules and crystalline surfaces is of great fundamental and technological interest and is extensively studied both experimentally and theoretically [1][2][3]. One particular example is physisorption and scattering of helium atoms on oxide surfaces. In the last two decades the latter process, employing molecular-beam techniques, has been developed into a powerful tool for the analysis of surface structure and dynamics [4][5][6][7][8]. It is particularly useful for studying insulating surfaces, such as MgO [4,9]. At close proximity the helium-surface interaction potential is dominated by the exponentially growing corrugated repulsive wall, which is a consequence of the mutual exchange repulsion between the helium and surface electron densities. The repulsive potential is two-dimensional (2D) corrugated and leads to a complicated diffraction pattern for helium scattered from the surface. In the range of intermediate He-surface distances, there exists a very shallow attractive potential due to the weak van der Waals interactions, which drops off with distance from the surface as 1/z 3 [10]. Such a potential can support several bound states (in fact several 2D bands of bound states), which correspond to vibrational levels of helium atoms physisorbed on the surface.The delicacy of the balance between different components of the helium-surface interaction makes quantitatively accurate theoretical predictions of the behavior of helium atoms on the surface extremely difficult. Standard density functional theory (DFT), which is the common tool in solid-state simulations (i.e., local-density approximation, generalized gradient approximation, or hybrids), does not capture van der Waals dispersion. In principle it can be used for calculating * r.martinezcasado@imperial.ac.uk † denis.usvyat@chemie.uni-regensburg.de the repulsive wall at th...

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Approaching the theoretical limit in periodic local MP2 calculations with atomic-orbital basis sets: The case of LiH

Cited by 55 publications

References 36 publications

Explicitly correlated plane waves: Accelerating convergence in periodic wavefunction expansions

Explicitly correlated plane waves: Accelerating convergence in periodic wavefunction expansions

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

Approaching an exact treatment of electronic correlations at solid surfaces: The binding energy of the lowest bound state of helium adsorbed on MgO(100)

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