Simplified continuum solvent model with a smooth cavity based on volumetric data

Held, Alexander; Walter, Michael

doi:10.1063/1.4900838

Cited by 80 publications

(110 citation statements)

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“…Other examples include the work of Scherlis and coworkers [83] and the model by Held and Walter. [84] As a downside, the spherical approximation at the core of the atomic interface may be inaccurate when the molecular electronic density is very different from the sum of atomic contributions. This is often the case when significant charge reorganizations occur in the system and electrons move from one atom to another, for example, in acidic hydrogens.…”

Section: Atomic Vs Electronic Interfacesmentioning

confidence: 99%

“…This contribution was later acquired by several other models, for example, Refs. [34,64,65,84] Defining the interface in terms of just the electronic density may present some significant drawbacks in specific applications. One critical limitation is encountered when using approximate techniques to handle core-electrons, such as the pseudo-potential approach commonly adopted in condensed-matter simulations based on delocalized basis sets.…”

Section: Atomic Vs Electronic Interfacesmentioning

confidence: 99%

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Continuum embeddings in condensed‐matter simulations

Andreussi

Fisicaro

2018

Int J of Quantum Chemistry

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Continuum models have a long tradition in computational chemistry, where they have provided a compact and efficient way to characterize environment effects in quantum-mechanical simulations of solvated systems. Fattebert and Gygi pioneered the development of continuum dielectric embedding schemes for periodic systems and their seamless extension toward molecular dynamics simulations. Following their work, continuum embedding approaches in condensedmatter simulations have thrived. The possibility to model wet and electrified interfaces, with a reduced computational overhead with respect to isolated systems, is opening new perspectives in the characterization of materials and devices. Important applications of these new techniques are in the field of catalysis, electro-chemistry, electro-catalysis, etc. Here we will address the main physical and computational aspects of continuum embedding schemes recently developed for condensed-matter simulations, underlying their peculiarities and their differences with respect to the quantum-chemistry state-of-the-art.condensed matter, continuum models, electro-chemistry, materials, solvation 1 | INTRODUCTION An embedding liquid environment can substantially affect the electronic properties, geometries and spectroscopic responses of the embedded system. Dealing with this kind of effects is a difficult computational task, due to the multiscale nature of the system. A brute force approach to handle these effects would require including all of the solvent atomistic details in the quantum-mechanical (QM) calculation of the solvated system. The total number of degrees of freedom, in particular the number of electrons that need to be described in a first-principles calculation, can thus increase by orders of magnitude. As a result, a calculation that would be feasible in vacuum can easily become untreatable in solution. Moreover, statistical sampling and averaging of the results over different configurations of the liquid would be required, thus further increasing the computational cost of such an approach. These limitations have motivated the development of incredibly powerful simulation programs, [1][2][3] able to take advantage of the rapid evolution of scientific computing hardware and software, for example, by fully exploiting parallel and hybrid architectures. Regardless of its computational feasibility, the explicit description of liquid environments may also suffer from some well-known limitations of current state-of-the-art ab initio methods, in particular regarding their structural [4][5][6][7] and dielectric [8][9][10] properties.On the other hand, when looking at the properties of a solvated system, it is often the case that the detailed effects caused by solute-solvent interactions are less important than the intrinsic properties of the solute. If this is the case, one can exploit a hierarchical approach, where solvent degrees of freedom are treated with a computationally less expensive technique, but are coupled with an highly accurate description of the solvated system...

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Section: Atomic Vs Electronic Interfacesmentioning

confidence: 99%

Section: Atomic Vs Electronic Interfacesmentioning

confidence: 99%

Continuum embeddings in condensed‐matter simulations

Andreussi

Fisicaro

2018

Int J of Quantum Chemistry

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“…31 Using this connection to fit the effective potential, only a single parameter is needed to predict the volumina of various test molecules in water in good agreement to experiment. 2 The cavity volume V C is obtained by an integration over the solvent excluded…”

Section: Clausius-mossotti Relation and Virtual Cavity Modelmentioning

confidence: 99%

“…Table 3 lists the cavity volumes V C and corresponding radii R C = (3V C /4π) 1/3 that were obtained from the cavity definition in the recently developed continuum solvent model implemented in the GPAW package. 2,30 The generally non-spherical cavity with a smooth boundary is obtained from an effective repulsive potential that describes the interaction between the continuum of the water solvent and the solute molecule. This potential leads to an effective solvent distribution function 0 ≤ g ≤ 1 that can be related to measurable partial molar volumes at the limit of infinite dilution through the compressibility equation.…”

Section: Clausius-mossotti Relation and Virtual Cavity Modelmentioning

confidence: 99%

“…The optical behaviour of small object dissolved in a medium are of interest for a large number of investigations, such as optofluids, 1 medium-assisted density-functional theory (DFT), 2 nanomedicine, 3 hydrogen storage, 4 bio-organics 5 and photodynamic therapy. 6 The impact of a cavity around the particles is large compared to the typically studied situations where the particles are considered without an environment.…”

Section: Introductionmentioning

confidence: 99%

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Effective Polarizability Models

et al. 2017

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Theories for the effective polarisability of a small particle in a medium are presented using different levels of approximation: we consider the virtual cavity, real cavity and the hard-sphere models as well as a continuous interpolation of the latter two. We present the respective hard-sphere and cavity radii as obtained from density-functional simulations as well as the resulting effective polarisabilities at discrete Matsubara frequencies. This enables us to account for macroscopic media in van der Waals interactions between molecules in water and their Casimir-Polder interaction with an interface.

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