Cooperative Effect of Hydrogen-Bonded Chains in the Environment of a π → π* Chromophore

Fradelos, Georgios; Kaminski, Jakub Wojciech; Wesołowski, Tomasz Adam; Leutwyler, Samuel

doi:10.1021/jp906483z

Cited by 17 publications

(32 citation statements)

References 34 publications

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“…5, and alternatively known as the "neglect of di↵erential response of the environment" (NDRE) approximation. 10 For the calculations with reconstructed potentials, the terms in the exchange-correlation-kinetic-energy kernel are approximately evaluated with the electron densities of the isolated subsystems. Tests without the embedding contribution in the exchange-correlation kernel confirm that these contributions are very small, even at the shortest distances considered here.…”

Section: Methodsmentioning

confidence: 99%

Excitation energies from frozen-density embedding with accurate embedding potentials

Artiukhin

Jacob

Neugebauer

2015

The Journal of Chemical Physics

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We present calculations of excitation energies within the time-dependent density functional theory (TDDFT) extension of frozen-density embedding (FDE) using reconstructed accurate embedding potentials. Previous applications of FDE showed significant deviations from supermolecular calculations; our current approach eliminates one potential error source and yields excitation energies of generally much better agreement with Kohn-Sham-TDDFT. Our results demonstrate that the embedding potentials represent the main error source in FDE-TDDFT calculations using standard approximate kinetic-energy functionals for excitations localized within one subsystem.

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Section: Methodsmentioning

confidence: 99%

Excitation energies from frozen-density embedding with accurate embedding potentials

Artiukhin

Jacob

Neugebauer

2015

The Journal of Chemical Physics

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“…Shortly after, Wesołowski implemented a simplified version of this subsystem‐based response theory, in which it is explicitly assumed that the response contribution from the environment (subsystem B ) is zero . This case, later called “uncoupled FDE” (FDEu) or “neglect of dynamic response of the environment” (NDRE), may be regarded as a strict FDE‐TDDFT variant, in which the environmental density is considered frozen also in the response framework. The corresponding response equation looks like that of the isolated system A , only that the orbitals and orbital energies are obtained under the influence of the effective embedding potential given in Eq.…”

Section: Property and Spectra Calculationsmentioning

confidence: 99%

“…Several studies investigated hydrogen‐bond–induced shifts in excitation energies. Fradelos et al demonstrated that the effect of an increasing number of solvent molecules in microsolvated cis ‐7‐hydroxyquinoline is highly non‐additive . For the same chromophore, it was later shown that solvatochromic shifts induced by hydrogen bonds are actually better described by FDEu than by supermolecular TDDFT calculations, taking equation‐of‐motion coupled cluster (EOM‐CC) calculations as a reference .…”

Section: Property and Spectra Calculationsmentioning

confidence: 99%

Subsystem density‐functional theory

Jacob

Neugebauer

2014

WIREs Comput Mol Sci

356

504

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Subsystem density-functional theory (subsystem DFT) has developed into a powerful alternative to Kohn-Sham DFT for quantum chemical calculations of complex systems. It exploits the idea of representing the total electron density as a sum of subsystem densities. The optimum total density is found by minimizing the total energy with respect to each of the subsystem densities, which breaks down the electronic-structure problem into effective subsystem problems. This enables calculations on large molecular aggregates and even (bio-)polymers without systemspecific parameterizations. We provide a concise review of the underlying theory, typical approximations, and embedding approaches related to subsystem DFT such as frozen-density embedding (FDE). Moreover, we discuss extensions and applications of subsystem DFT and FDE to molecular property calculations, excited states, and wave function in DFT embedding methods. Furthermore, we outline recent developments for reconstruction techniques of embedding potentials arising in subsystem DFT, and for using subsystem DFT to incorporate constraints into DFT calculations. C 2013 John Wiley & Sons, Ltd.

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“…The geometries of the considered ''microsolvated'' cis-7-hydroxyquinoline clusters are also taken from Refs. [47,87].…”

Section: Cis-7-hydroxyquinoline In Hydrogen-bonded Complexesmentioning

confidence: 99%

“…The geometries of these complexes are taken from Refs. [47,87], which provide also reference benchmark shifts from EOM-CC and FDET calculations. The chosen systems represent well the worst scenario as far as the approximation introduced in Eq.…”

Section: Superposition Of Molecular Densitiesmentioning

confidence: 99%

How to choose the frozen density in Frozen-Density Embedding Theory-based numerical simulations of local excitations?

et al. 2013

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According to Frozen-Density Embedding Theory, any observable evaluated for the embedded species is a functional of the frozen density (ρB —the density associated with the environment). The environment-induced shifts in the energies of local excitations in organic chromophores embedded in hydrogen-bonded environments are analyzed. The excitation energies obtained for ρB , which is derived from ground-state calculations for the whole environment applying medium quality basis sets (STO–DZP) or larger, vary in a narrow range (about 0.02 eV which is at least one order of magnitude less than the magnitude of the shift). At the same time, the ground-state dipole moment of the environment varies significantly. The lack of correlation between the calculated shift and the dipole moment of the environment reflects the fact that, in Frozen-Density Embedding Theory, the partitioning of the total density is not unique. As a consequence, such concepts as “environment polarization” are not well defined within Frozen-Density Embedding Theory. Other strategies to generate ρB (superposition of densities of atoms/molecules in the environment) are shown to be less robust for simulating excitation energy shifts for chromophores in environments comprising hydrogen-bonded molecules

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Cooperative Effect of Hydrogen-Bonded Chains in the Environment of a π → π* Chromophore

Cited by 17 publications

References 34 publications

Excitation energies from frozen-density embedding with accurate embedding potentials

Excitation energies from frozen-density embedding with accurate embedding potentials

Subsystem density‐functional theory

How to choose the frozen density in Frozen-Density Embedding Theory-based numerical simulations of local excitations?

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