Molecular properties via a subsystem density functional theory formulation: A common framework for electronic embedding

Höfener, Sebastian; Gomes, André Severo Pereira; Visscher, Lucas

doi:10.1063/1.3675845

Cited by 108 publications

(127 citation statements)

References 81 publications

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“…In particular, WFT-in-DFT embedding utilizes the theoretical framework of DFT embedding to enable the WFT description of a given subsystem in the effective potential that is created by the remaining electronic density of the system. [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] We recently introduced a simple, projection-based method for performing accurate WFT-in-DFT embedding calculations 30 that avoids the need for a numerically challenging optimized effective potential (OEP) calculation 24,25,[31][32][33][34] via the introduction of a level-shift operator. It was shown that this method enables the accurate calculation of WFT-in-DFT subsystem correlation energies, as well as many-body expansions (MBEs) of the total WFT correlation energy.…”

Section: Introductionmentioning

confidence: 99%

“…Among these are the QM/MM, [1][2][3][4][5][6] ONIOM, 7,8 fragment molecular orbital (FMO), [9][10][11][12][13][14][15] and wavefunction theory (WFT)-in-density functional theory (DFT) embedding [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] approaches, which allow for the treatment of systems that would not be practical using conventional WFT approaches. In particular, WFT-in-DFT embedding utilizes the theoretical framework of DFT embedding to enable the WFT description of a given subsystem in the effective potential that is created by the remaining electronic density of the system.…”

Section: Introductionmentioning

confidence: 99%

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Accurate basis set truncation for wavefunction embedding

Barnes

Goodpaster

Manby³

et al. 2013

The Journal of Chemical Physics

127

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Density functional theory (DFT) provides a formally exact framework for performing embedded subsystem electronic structure calculations, including DFT-in-DFT and wavefunction theory-in-DFT descriptions. In the interest of efficiency, it is desirable to truncate the atomic orbital basis set in which the subsystem calculation is performed, thus avoiding high-order scaling with respect to the size of the MO virtual space. In this study, we extend a recently introduced projection-based embedding method [F. R. Manby, M. Stella, J. D. Goodpaster, and T. F. Miller III, J. Chem. Theory Comput. 8, 2564 (2012)] to allow for the systematic and accurate truncation of the embedded subsystem basis set. The approach is applied to both covalently and non-covalently bound test cases, including water clusters and polypeptide chains, and it is demonstrated that errors associated with basis set truncation are controllable to well within chemical accuracy. Furthermore, we show that this approach allows for switching between accurate projection-based embedding and DFT embedding with approximate kinetic energy (KE) functionals; in this sense, the approach provides a means of systematically improving upon the use of approximate KE functionals in DFT embedding. © 2013 AIP Publishing LLC. [http://dx

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Accurate basis set truncation for wavefunction embedding

Barnes

Goodpaster

Manby³

et al. 2013

The Journal of Chemical Physics

127

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“…Table 3. Solvatochromic shifts (in eV), oscillator strengths (in atomic units), and weight of the lowest π → π * orbital transition of pNA in (H 2 O) 18 cluster, obtained using TD-EMFT with mixedbasis B3LYP-in-LDA and B3LYP-in-FCLDA embedding, and TDDFT at the B3LYP/6-31G* and LDA/STO-3G levels of theory. The solvatochromic shifts are computed relative to the gas-phase results, which are obtained using TDDFT with B3LYP/6-31G* for the bare pNA molecule.…”

Section: Computational Detailsmentioning

confidence: 99%

“…For example, linear-scaling implementations based on linear response take advantage of spatial locality of either the atomic [5][6][7] or molecular [8][9][10][11][12][13] orbitals. An alternative strategy employs subsystem embedding to describe localized excitations, including TDDFT implementations using either fragment molecular orbitals 14 or frozen-density embedding, [15][16][17][18][19][20] as well as the QM/MM approach. [21][22][23][24] While each of these methods has merits, they also have limitations.…”

Section: Introductionmentioning

confidence: 99%

Linear-Response Time-Dependent Embedded Mean-Field Theory

Ding

Tsuchiya

Manby

et al. 2017

J. Chem. Theory Comput.

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We present a time-dependent (TD) linear-response description of excited electronic states within the framework of embedded mean-field theory (EMFT). TD-EMFT allows for subsystems to be described at different mean-field levels of theory, enabling straightforward treatment of excited-states and transition properties. We provide benchmark demonstrations of TD-EMFT for both local and non-local excitations in organic molecules, as well as applications to chlorophyll a, solvatochromic shifts of a dye in solution, and sulfur K-edge X-ray absorption spectroscopy (XAS). It is found that mixed-basis implementations of TD-EMFT lead to substantial errors in terms of transition properties; however, as previously found for ground-state EMFT, these errors are largely eliminated with the use of Fock-matrix corrections. These results indicate that TD-EMFT is a promising method for the efficient, multi-level description of excitedstate electronic structure and dynamics in complex systems.

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“…This type of approach has been applied successfully in describing the effect of chloride-actinyl interactions on the f-f spectra of the NpO 2+ 2 cation. 46 The WFT-in-DFT frozen density embedding (FDE) scheme is theoretically well-defined and suitable for extension to coupled subsystems 47 and can provide an enormous reduction of both computational cost and the complexity of the data that is to be analyzed. We therefore think it is of interest to use the CUO noble gas interaction as another test case for the feasibility of the approach in describing uranium coordination chemistry.…”

Section: Introductionmentioning

confidence: 99%

The electronic spectrum of CUONg4 (Ng = Ne, Ar, Kr, Xe): New insights in the interaction of the CUO molecule with noble gas matrices

Tecmer¹,

Lingen²,

Gomes

et al. 2012

The Journal of Chemical Physics

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The electronic spectrum of the CUO molecule was investigated with the IHFSCC-SD (intermediate Hamiltonian Fock-space coupled cluster with singles and doubles) method and with TD-DFT (timedependent density functional theory) employing the PBE and PBE0 exchange-correlation functionals. The importance of both spin-orbit coupling and correlation effects on the low-lying excitedstates of this molecule are analyzed and discussed. Noble gas matrix effects on the energy ordering and vibrational frequencies of the lowest electronic states of the CUO molecule were investigated with density functional theory (DFT) and TD-DFT in a supermolecular as well as a frozen density embedding (FDE) subsystem approach. This data is used to test the suitability of the FDE approach to model the influence of different matrices on the vertical electronic transitions of this molecule. The most suitable potential was chosen to perform relativistic wave function theory in density functional theory calculations to study the vertical electronic spectra of the CUO and CUONg 4 with the IHFSCC-SD method.

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Molecular properties via a subsystem density functional theory formulation: A common framework for electronic embedding

Cited by 108 publications

References 81 publications

Accurate basis set truncation for wavefunction embedding

Accurate basis set truncation for wavefunction embedding

Linear-Response Time-Dependent Embedded Mean-Field Theory

The electronic spectrum of CUONg4 (Ng = Ne, Ar, Kr, Xe): New insights in the interaction of the CUO molecule with noble gas matrices

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