Towards an exact description of electronic wavefunctions in real solids

Booth, George H.; Grüneis, Andreas; Kresse, Georg; Alavi, Ali

doi:10.1038/nature11770

Cited by 516 publications

(538 citation statements)

References 43 publications

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“…This problem is commonly treated with brute force full configuration interaction (FCI), 13 which is practical for up to approximately 16 active orbitals. However, recently significant progress has been made with alternative methods to FCI; in particular, due to developments in the density matrix renormalization group (DMRG) algorithm, FCI Quantum Monte Carlo (FCIQMC), [14][15][16] and selected configuration interaction approaches [17][18][19] , static correlation can now be treated accurately in much larger active spaces. We here focus on DMRG, 20,21 a variational method which minimizes the energy of a wavefunction parametrized as a matrix product state (MPS).…”

Section: Introductionmentioning

confidence: 99%

Combining Internally Contracted States and Matrix Product States To Perform Multireference Perturbation Theory

Sharma

Knizia

Guo

et al. 2017

J. Chem. Theory Comput.

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We present two efficient and intruder-free methods for treating dynamic correlation on top of general multi-configuration reference wave functions-including such as obtained by the density matrix renormalization group (DMRG) with large active spaces. The new methods are the second order variant of the recently proposed multi-reference linearized coupled cluster method (MRLCC) [S. Sharma, A. Alavi, J. Chem. Phys. 143, 102815 (2015)], and of N-electron valence perturbation theory (NEVPT2), with expected accuracies similar to MRCI+Q and (at least) CASPT2, respectively. Great efficiency gains are realized by representing the first-order wave function with a combination of internal contraction (IC) and matrix product state perturbation theory (MPSPT). With this combination, only third order reduced density matrices (RDMs) are required. Thus, we obviate the need for calculating (or estimating) RDMs of fourth or higher order; these had so far posed a severe bottleneck for dynamic correlation treatments involving the large active spaces accessible to DMRG. Using several benchmark systems, including first and second row containing small molecules, Cr2, pentacene and oxo-Mn(Salen), we shown that active spaces containing at least 30 orbitals can be treated using this method. On a single node, MRLCC2 and NEVPT2 calculations can be performed with over 550 and 1100 virtual orbitals, respectively. We also critically examine the errors incurred due to the three sources of errors introduced in the present implementation -calculating second order instead of third order energy corrections, use of internal contraction and approximations made in the reference wavefunction due to DMRG.

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Section: Introductionmentioning

confidence: 99%

Combining Internally Contracted States and Matrix Product States To Perform Multireference Perturbation Theory

Sharma

Knizia

Guo

et al. 2017

J. Chem. Theory Comput.

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“…Recently, several methods such as MP2, couple cluster theory and full configuration interaction quantum Monte Carlo have been successfully applied to periodic systems. [27,28] However, their heavy computational cost still prevents them from being used for almost all MOFs of current interest. It is evident from the large amount of current research that is focusing on these two aspects that both directions will continue to be explored simultaneously in the near term.…”

Section: Discussionmentioning

confidence: 99%

Thermodynamics of gas adsorption in MOFs using Ab Initio calculations

Poloni

Kim

2015

Int J of Quantum Chemistry

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Metal-organic frameworks (MOFs) are attracting much attention as promising materials for gas separation. Given the large number of design possibilities in the MOF materials space, it is desirable to efficiently characterize their performance prior to their experimental synthesis. This Perspective focuses on some of the works that have been put forth in developing new methods that accurately describe the thermodynamics of gas uptake in MOFs by making use of a few selected ab initio calculations. We provide a future outlook toward a full ab initio description of these properties using efficient sampling strategies in conjunction with faster and more accurate quantum methods.

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“…Such a situation calls for an ab initio treatment in which the exact answer can be approached systematically. It is only very recently that such a treatment became applicable to periodic systems [20,21].For the He-MgO(100) system there are several experimental studies in the literature reporting the energy of the ground state of adsorbed He [4,18,22,23]. In adsorption isotherm measurements of MgO smoke [23], a value of −4.8 meV for the adsorption energy was obtained.…”

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confidence: 99%

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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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Towards an exact description of electronic wavefunctions in real solids

Cited by 516 publications

References 43 publications

Combining Internally Contracted States and Matrix Product States To Perform Multireference Perturbation Theory

Combining Internally Contracted States and Matrix Product States To Perform Multireference Perturbation Theory

Thermodynamics of gas adsorption in MOFs using Ab Initio calculations

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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