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

Usvyat, Denis

doi:10.1063/1.4829898

Cited by 46 publications

(54 citation statements)

References 120 publications

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“…42,44,45,120,121,158 Alternatively, it is possible to employ Gaussian basis sets in explicitly correlated theory for solids. 129,159 The main advantage of this approach is that one can exploit the framework developed in F12 theory for many-electron integrals in conjunction with the local correlation techniques described in Sec. III.…”

Section: Explicitly Correlated Plane Wavesmentioning

confidence: 99%

Perspective: Explicitly correlated electronic structure theory for complex systems

Grüneis

Hirata

Ohnishi

et al. 2017

The Journal of Chemical Physics

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The explicitly correlated approach is one of the most important breakthroughs in ab initio electronic structure theory, providing arguably the most compact, accurate, and efficient ansatz for describing the correlated motion of electrons. Since Hylleraas first used an explicitly correlated wave function for the He atom in 1929, numerous attempts have been made to tackle the significant challenges involved in constructing practical explicitly correlated methods that are applicable to larger systems. These include identifying suitable mathematical forms of a correlated wave function and an efficient evaluation of many-electron integrals. R12 theory, which employs the resolution of the identity approximation, emerged in 1985, followed by the introduction of novel correlation factors and wave function ansätze, leading to the establishment of F12 theory in the 2000s. Rapid progress in recent years has significantly extended the application range of explicitly correlated theory, offering the potential of an accurate wave-function treatment of complex systems such as photosystems and semiconductors. This perspective surveys explicitly correlated electronic structure theory, with an emphasis on recent stochastic and deterministic approaches that hold significant promise for applications to large and complex systems including solids. Published by AIP Publishing. [http://dx

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Section: Explicitly Correlated Plane Wavesmentioning

confidence: 99%

Perspective: Explicitly correlated electronic structure theory for complex systems

Grüneis

Hirata

Ohnishi

et al. 2017

The Journal of Chemical Physics

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“…Metals were not considered in this study since the perturbative nature of the MP2 approach does not allow calculations on systems with a very small or zero band gap. 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.…”

Section: Computational Details a Test Systemsmentioning

confidence: 99%

“…14 Concerning the study of solids, we note that the introduction of wave-function-based correlation treatment for periodic systems is relatively recent. [18][19][20][21][22][23][24][25][26] Martinez-Casado and a) lorenzo.maschio@unito.it coworkers proposed to estimate the correlation energy as a MP2 contribution using a B3LYP reference state and applied this scheme to the study of the adsorption of helium atoms on a MgO surface. 27 Del Ben and coworkers 24 benchmarked the performance of some global double hybrids on a set of molecular crystals.…”

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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“…The basis set error correction was evaluated also in the periodic framework, employing the recently implemented periodic LMP2-F12 method [36] in the 3 * A fixed-amplitude approximation [49][50][51]. The periodic F12 correction was evaluated using a three-layer MgO slab.…”

Section: Appendix D: Incremental Ccsd(t) Correction To the Periodic Lmentioning

confidence: 99%

“…(iv) Finally, to check the quality of the correction protocol for improving the periodic LMP2 approach, a single point calculation at the on-Mg site geometry (minimum-energy z position) was carried out, adopting an alternative, more rigorous, but also much more expensive correction protocol: the basis set correction was included in the periodic rather than in the finite cluster calculation by utilizing the recently implemented periodic LMP-F12 method [36]; the incremental CCSD(T)-LMP2 correction [16,37,38] was evaluated for a rather large He-Mg 9 O 9 cluster in a rich basis set [cc-pVTZ(Mg)/augcc-pVTZ(O)/aug-cc-pVQZ(He)]; those oxygen-helium pair energies not contained in the Mg 9 O 9 -He cluster were upscaled in the periodic LMP2-F12 calculation by the previous factor of 1.7, i.e., according to Table I. This model yields a well depth of −10.3 meV for the on-Mg site, nearly 2 meV higher than the one predicted by the original correction protocol used for evaluating the PES.…”

Section: Ups1mentioning

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

Cited by 46 publications

References 120 publications

Perspective: Explicitly correlated electronic structure theory for complex systems

Perspective: Explicitly correlated electronic structure theory for complex systems

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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