Communication: Density functional theory embedding with the orthogonality constrained basis set expansion procedure

Culpitt, Tanner; Brorsen, Kurt R.; Hammes‐Schiffer, Sharon

doi:10.1063/1.4984777

Cited by 47 publications

(62 citation statements)

References 33 publications

(22 reference statements)

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“…MCP, methylenecyclopropene; LUMO, lowest unoccupied molecular orbital basis-set expansion used in the embedding context to keep orbitals of different subsystems orthogonal. [43] Transforming the embedded Fock matrix of subsystem A (F A(Env) ) in the space spanned by the selected virtual orbitals…”

Section: Theoretical Backgroundmentioning

confidence: 99%

“…Because of the fact that the intra‐subsystem Fock matrix is not diagonalized by the rotated orbitals, an additional diagonalization is necessary. Note that this procedure is similar to the orthogonality‐constrained basis‐set expansion used in the embedding context to keep orbitals of different subsystems orthogonal 43 . Transforming the embedded Fock matrix of subsystem A ( F A(Env) ) in the space spanned by the selected virtual orbitals

F^{A} = {\overset{false˜}{boldC}}_{virt}^{normalA, T} F^{normalA ((), Env)} {\overset{false˜}{boldC}}_{virt}^{A}

yields a new set of eigenvectors

C^{A}

and eigenvalues via diagonalization of

F^{A}

.…”

Section: Theoretical Backgroundmentioning

confidence: 99%

See 1 more Smart Citation

Analysis of environment response effects on excitation energies within subsystem‐based time‐dependent density‐functional theory

Scholz

Tölle

Neugebauer

2020

Int J of Quantum Chemistry

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Section: Theoretical Backgroundmentioning

confidence: 99%

F^{A} = {\overset{false˜}{boldC}}_{virt}^{normalA, T} F^{normalA ((), Env)} {\overset{false˜}{boldC}}_{virt}^{A}

yields a new set of eigenvectors

C^{A}

and eigenvalues via diagonalization of

F^{A}

.…”

Section: Theoretical Backgroundmentioning

confidence: 99%

Analysis of environment response effects on excitation energies within subsystem‐based time‐dependent density‐functional theory

Scholz

Tölle

Neugebauer

2020

Int J of Quantum Chemistry

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show abstract

“…1, red). Errors associated with finite values of µ can also be avoided by enforcing the projection via explicit orthogonalization [52][53][54][55][56] of the subsystem orbitals, at some cost to the simplicity of the implementation.…”

Section: Dft-in-dft Embeddingmentioning

confidence: 99%

Projection-Based Wavefunction-in-DFT Embedding

Lee¹,

Welborn

Manby³

et al. 2019

Acc. Chem. Res.

121

153

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Complex chemical systems present challenges to electronic structure theory, stemming from large system sizes, subtle interactions, coupled dynamical timescales, or electronically nonadiabatic effects. New methods are needed to perform reliable, rigorous, and affordable electronic structure calculations for simulating the properties and dynamics of such systems. This Account reviews projection-based quantum embedding for electronic structure. The method provides a simple, robust, and accurate approach for describing a small part of a chemical system at the level of a correlated wavefunction (WF) method while the remainder of the system is described at the level of density functional theory (DFT). We present the theoretical underpinnings of projection-based embedding, describe use of the method for combining wavefunction and density-functional theories, and discuss technical refinements that have improved the applicability and robustness of the method. Applications of projection-based WFin-DFT embedding are also reviewed, with particular focus on recent work on transition-metal catalysis, enzyme reactivity, and battery electrolyte decomposition. Looking forward, we anticipate continued refinement of the projectionbased embedding methodology, as well as increasingly widespread application in diverse areas of chemistry, biology, and materials science.

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“…The orthogonality of the P and Q spaces reflects in the orthogonality of the original χ i and Qξ functions, but that orthogonality is lost when we act on χ i and on Qξ with Θ 1 2 (µ−H) in Eqs. (14), (16). Further note that, as mentioned, the same overall Hamiltonian (and therefore the same Θ 1 2 (µ − H) ) is used in preparing both the stochastic and deterministic orbitals, i.e., they are treated on equal footing.…”

Section: B Dft Embeddingmentioning

confidence: 99%

Stochastic embedding DFT: Theory and application to p-nitroaniline in water

Chen

Rabani

et al. 2019

The Journal of Chemical Physics

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Over this past decade, we combined the idea of stochastic resolution of identity with a variety of electronic structure methods. In our stochastic Kohn-Sham DFT method, the density is an average over multiple stochastic samples, with stochastic errors that decrease as the inverse square root of the number of sampling orbitals. Here we develop a stochastic embedding density functional theory method (se-DFT) that selectively reduces the stochastic error (specifically on the forces) for a selected sub-system(s). The motivation, similar to that of other quantum embedding methods, is that for many systems of practical interest the properties are often determined by only a small sub-system. In stochastic embedding DFT two sets of orbitals are used: a deterministic one associated with the embedded subspace, and the rest which is described by a stochastic set. The method is exact in the limit of large number of stochastic samples. We apply se-DFT to study a p-nitroaniline molecule in water, where the statistical errors in the forces on the system (the p-nitroaniline molecule) are reduced by an order of magnitude compared with non-embedding stochastic DFT.

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Communication: Density functional theory embedding with the orthogonality constrained basis set expansion procedure

Abstract: Communication: A novel implementation to compute MP2 correlation energies without basis set superposition errors and complete basis set extrapolation

Cited by 47 publications

References 33 publications

Analysis of environment response effects on excitation energies within subsystem‐based time‐dependent density‐functional theory

Analysis of environment response effects on excitation energies within subsystem‐based time‐dependent density‐functional theory

Projection-Based Wavefunction-in-DFT Embedding

Stochastic embedding DFT: Theory and application to p-nitroaniline in water

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