Density functional theory based embedding approaches for transition-metal complexes

Bensberg, Moritz; Neugebauer, Johannes

doi:10.1039/d0cp05188h

Cited by 19 publications

(27 citation statements)

References 63 publications

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“…In the case of the M06 functional, we believe the slight increase in error by 2 kcal/mol is due to the fact that the M06 functional closely recreates the WF results on its own and embedding introduces minor errors for small subsystem divisions as we have seen previously. Some embedding error for small WF subsystem sizes is expected however, and has been well documented by Bensberg and Neugebauer in a recent article 55 When looking at the strong field system shown in Fig. 6, it is clear that expanding the WF region does significantly improve the embedding results and in every case more closely recreates the UCCSD(T) results than the corresponding XC functional.…”

Section: Spin Transition Energysupporting

confidence: 59%

“…Projection operator based DFT embedding has been developed by many groups with significant success. [44][45][46][47][48][49][50][51][52][53][54][55] Recent work in our group has focused on Huzinaga level-shift projection operator DFT embedding in the absolutely localized basis. We have demonstrated the efficiency, accuracy, and systematic improvability of this method for closed-shell molecular ground 56,57 and excited states, 18 and ground state properties of periodic systems.…”

Section: Introductionmentioning

confidence: 99%

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Huzinaga Projection Embedding for Efficient and Accurate Energies of Systems with Localized Spin-densities

Graham

Wen

Chulhai

et al. 2021

Preprint

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We demonstrate the accuracy and efficiency of the restricted open-shell and unrestricted formulation of the absolutely localized Huzinaga projection operator embedding method. Restricted open-shell and unrestricted Huzinaga projection embedding in the full system basis is formally exact to restricted open-shell and unrestricted Kohn-Sham density functional theory, respectively. By utilizing the absolutely localized basis, we significantly improve the efficiency of the method, while maintaining high accuracy. The open-shell embedding method is shown to calculate electronic energies of a variety of systems to within 1 kcal/mol accuracy of the full system wave function result. For certain highly localized reactions, such as spin transition energies on transition metals, we find that very few atoms are necessary to include in the wave function region, in order to achieve desired accuracy. Here we apply our method to several representative examples such as spin splitting energies, catalysis on transition metals, and radical reactions.

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Section: Spin Transition Energysupporting

confidence: 59%

Section: Introductionmentioning

confidence: 99%

Huzinaga Projection Embedding for Efficient and Accurate Energies of Systems with Localized Spin-densities

Graham

Wen

Chulhai

et al. 2021

Preprint

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“…The choice of the functionals used for the non‐additive exchange‐correlation energy potential can also be relevant. For instance, systems including transition metals may require the use of double‐hybrid exchange‐correlation functionals [67], or long‐range corrections [62].…”

Section: Resultsmentioning

confidence: 99%

Relativistic frozen density embedding calculations of solvent effects on the nuclear magnetic resonance shielding constants of transition metal nuclei

Olejniczak

Antušek

Jaszuński

2021

Int J of Quantum Chemistry

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Nuclear magnetic resonance shielding constants of transition metals in solvated complexes are computed at the relativistic density functional theory (DFT) level. The solvent effects evaluated with subsystem‐DFT approaches are compared with the reference solvent shifts predicted from supermolecular calculations. Two subsystem‐DFT approaches are analyzed—in the standard frozen density embedding (FDE) scheme the transition metal complexes are embedded in an environment of solvent molecules whose density is kept frozen, in the second approach the densities of the complex and of its environment are relaxed in the “freeze‐and‐thaw” procedure. The latter approach improves the description of the solvent effects in most cases, nevertheless the FDE deficiencies are rather large in some cases.

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“…Molecular interactions may be accurately described with high level molecular orbital theories (e.g., coupled cluster theory [ 37 , 38 ]) or sophisticated density functionals combined with large basis sets [ 39 , 40 , 41 , 42 , 43 ]. However, such quantum mechanically detailed computation is prohibitively expensive for any realistic complex molecular systems.…”

Section: Challenges In Molecular Modelingmentioning

confidence: 99%

“Dividing and Conquering” and “Caching” in Molecular Modeling

Cao

Tian

2021

IJMS

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Molecular modeling is widely utilized in subjects including but not limited to physics, chemistry, biology, materials science and engineering. Impressive progress has been made in development of theories, algorithms and software packages. To divide and conquer, and to cache intermediate results have been long standing principles in development of algorithms. Not surprisingly, most important methodological advancements in more than half century of molecular modeling are various implementations of these two fundamental principles. In the mainstream classical computational molecular science, tremendous efforts have been invested on two lines of algorithm development. The first is coarse graining, which is to represent multiple basic particles in higher resolution modeling as a single larger and softer particle in lower resolution counterpart, with resulting force fields of partial transferability at the expense of some information loss. The second is enhanced sampling, which realizes “dividing and conquering” and/or “caching” in configurational space with focus either on reaction coordinates and collective variables as in metadynamics and related algorithms, or on the transition matrix and state discretization as in Markov state models. For this line of algorithms, spatial resolution is maintained but results are not transferable. Deep learning has been utilized to realize more efficient and accurate ways of “dividing and conquering” and “caching” along these two lines of algorithmic research. We proposed and demonstrated the local free energy landscape approach, a new framework for classical computational molecular science. This framework is based on a third class of algorithm that facilitates molecular modeling through partially transferable in resolution “caching” of distributions for local clusters of molecular degrees of freedom. Differences, connections and potential interactions among these three algorithmic directions are discussed, with the hope to stimulate development of more elegant, efficient and reliable formulations and algorithms for “dividing and conquering” and “caching” in complex molecular systems.

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Density functional theory based embedding approaches for transition-metal complexes

Abstract: Density functional theory based embedding approaches for the description of chemical reactions are reviewed for their applicability to transition metal species.

Cited by 19 publications

References 63 publications

Huzinaga Projection Embedding for Efficient and Accurate Energies of Systems with Localized Spin-densities

Huzinaga Projection Embedding for Efficient and Accurate Energies of Systems with Localized Spin-densities

Relativistic frozen density embedding calculations of solvent effects on the nuclear magnetic resonance shielding constants of transition metal nuclei

“Dividing and Conquering” and “Caching” in Molecular Modeling

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