Frozen density embedding with non-integer subsystems' particle numbers.

@article{Fabiano2014FrozenDE,
  title={Frozen density embedding with non-integer subsystems' particle numbers.},
  author={Eduardo Fabiano and Savio Laricchia and Fabio Della Sala},
  journal={The Journal of chemical physics},
  year={2014},
  volume={140 11},
  pages={
          114101
        }
}
We extend the frozen density embedding theory to non-integer subsystems' particles numbers. Different features of this formulation are discussed, with special concern for approximate embedding calculations. In particular, we highlight the relation between the non-integer particle-number partition scheme and the resulting embedding errors. Finally, we provide a discussion of the implications of the present theory for the derivative discontinuity issue and the calculation of chemical reactivity… 
View on PubMed
arxiv.org
16 Citations

Figures from this paper

16 Citations

Frozen-Density Embedding Strategy for Multilevel Simulations of Electronic Structure.

Modeling properties of chemical species and chemical reactions requires usually the quantum-mechanical level of description, and nonlocal embedding operators based on either transferrable pseudopotentials or frozen orbitals obtained from localization procedures have been developed in many groups.

Density embedding with constrained chemical potential

We formulate a chemical-potential constrained density embedding method for systems where different fragments can have either continuum or discrete electronic states. We illustrate the method with the…

Charge transfer excitations from exact and approximate ensemble Kohn-Sham theory.

It is shown that components of Kohn-Sham ensembles can be used to describe charge transfer processes and the approximate excitation energies obtained by using the exact ensemble densities in the recently formulated ensemble Hartree-exchange theory are computed.

eQE: An open‐source density functional embedding theory code for the condensed phase

In this work, we present the main features and algorithmic details of a novel implementation of the frozen density embedding (FDE) formulation of subsystem density functional theory (DFT) that is…

Partition density functional theory

A PDFT functional is developed to address the issues of static correlation and delocalization errors in PDFT and an approximation for the non-additive kinetic energy is introduced and shown how this quantity can be computed exactly.

Split electrons in partition density functional theory.

Partition density functional theory is a density embedding method that partitions a molecule into fragments by minimizing the sum of fragment energies subject to a local density constraint and a…

Accurate Reference Data for the Nonadditive, Noninteracting Kinetic Energy in Covalent Bonds.

It is found that the von Weizsäcker approximation can provide accurate NAKE in stretched covalent bonds, especially in the cases of Li2 and Na2.

Density-based partitioning methods for ground-state molecular calculations.

This work derives a new exact condition determining the strength of the singularities of the partition potentials at the nuclei, establishes the connection between charge-transfer and electronegativity equalization between fragments, and outlines a general strategy for overcoming delocalization and static-correlation errors in density-functional calculations.

Subsystem density-functional theory as an effective tool for modeling ground and excited states, their dynamics and many-body interactions

This topical review focuses on some recent advances in this field related to the computation of condensed phase systems, their excited states, and the evaluation of many-body interactions between the subsystems.

Laplacian-dependent models of the kinetic energy density: Applications in subsystem density functional theory with meta-generalized gradient approximation functionals.

A two-dimensional scan of semilocal KED models as linear functionals of the reduced gradient and of the reduction Laplacian, for atoms and weakly bound molecular systems is presented.

References

SHOWING 1-10 OF 95 REFERENCES

Self-consistent embedding theory for locally correlated configuration interaction wave functions in condensed matter.

This work presents new developments on a density-based embedding strategy for the electronic structure of localized feature in periodic, metallic systems and demonstrates how dynamical correlation effects can be treated within this embedding framework via the multireference singles and doubles configuration interaction method.

Frozen density embedding calculations with the orbital-dependent localized Hartree-Fock Kohn-Sham potential

Modelling charge transfer reactions with the frozen density embedding formalism.

Charge-localized, diabatic states are generated directly with FDE and used to calculate electronic couplings of hole transfer reactions in two π-stacked nucleobase dimers of B-DNA: 5'-GG-3' and 5'-GT-3'.

Semiclassical neutral atom as a reference system in density functional theory.

We use the asymptotic expansions of the semiclassical neutral atom as a reference system in density functional theory to construct accurate generalized gradient approximations (GGAs) for the…

Comment on "Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds" [J. Chem. Phys. 132, 164101 (2010)].

The authors do not distinguish between two different quantities: the functional and the potential, i.e., the correspondence assigning the non-additive kinetic potential to a pair of electron densities and the function (the potential itself).

Discontinuities of the exchange-correlation kernel and charge-transfer excitations in time-dependent density-functional theory

We identify the key property that the exchange-correlation (XC) kernel of time-dependent density functional theory must have in order to describe long-range charge-transfer excitations. We show that…

Frozen density embedding with hybrid functionals.

The Kohn-Sham equations with constrained electron density are extended to hybrid exchange-correlation (XC) functionals and it is found that the use of hybrid functionals leads to a significant improvement in the description of ground-state electronic properties of the investigated systems.

Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds.

The frozen-density embedding (FDE) scheme [Wesolowski and Warshel, J. Phys. Chem. 97, 8050 (1993)] relies on the use of approximations for the kinetic-energy component v(T)[rho(1),rho(2)] of the…

Density Functional Partition Theory with Fractional Occupations.

This work gives the full formalism of density functional partition theory (DFPT) and illustrates DFPT in the general case of noninteger fragment occupations.

Effect of discontinuities in Kohn-Sham-based chemical reactivity theory.

It is shown that in order to correctly measure the reactivity toward a nucleophilic reagent a discontinuity of the XC kernel has to be taken into account.
...