Source function and plane waves: Toward complete bader analysis

Tantardini, Christian; Ceresoli, Davide; Benassi, Enrico

doi:10.1002/jcc.24433

Cited by 8 publications

(10 citation statements)

References 52 publications

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“…This phase of fluorine is experimentally known to be characterized by disordered crystal structure with a Pm3̅ n space group. 55 Crystal data of considered structures are presented in Table S1, Supporting Information. Several local structures of β-fluorine were constructed based on the average disordered structure from an experiment by Jordan et al 59 We found that all the calculated β-fluorine approximants have similar energies.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Crystal Structure Evolution of Fluorine under High Pressure

2022

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Fluorinated compounds in the last decade were applied as photo-thermo-refractive glasses, high-stress lubricants, and pharmaceutical drugs due to their good mechanical properties and biocompatibility. Although fluorinated materials are largely employed, the possibility of predicting new structures was limited by the impossibility to use density functional theory (DFT) to describe interatomic and intermolecular interactions correctly. This is seen linearly to increase with fluorine concentration. In crystal structure prediction, modern algorithms are usually combined with first-principles methods employed for global solution, which sometimes fail to describe systems as in the case of strongly correlated materials. Fluorine is one of the tricky elements, which is characterized by relativistic effects and no overlap between the DFT exchange hole and the exact exchange hole. Thus, no relativistic exchange–correlation functional was seen to adequately describe fluorine. In this work, we have found an excellent compromise to investigate fluorinated materials using a combination of SCAN (exchange) and rVV10 (correlation) functionals. This was found through the fundamental study of α- and β-fluorine phases, showing α-fluorine as the most stable structure at temperatures lower than 35 K and 0 GPa with respect to β-fluorine. Further, we have computed crystal structure evolution under pressure looking for new stable fluorine allotropes using the USPEX evolutionary algorithm coupled with the SCAN-rVV10 exchange–correlation functional discovering two phase transitions: one from C2/c (i.e., α-fluorine) to Cmca at ∼5.5 GPa and from Cmca to the P4̅21 c phase at 220 GPa; all these structures possess metallic behavior. The achievements of this work lie far beyond the thermodynamic of fluorine crystals under pressure. It will give the right instrument to understand the chemical behavior of fluorinated materials under pressure with consequent great speed up to the crystal structure prediction of fluorinated and fluorine-based materials.

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Section: ■ Results and Discussionmentioning

confidence: 99%

“…It is worth noting that a feasible approach to treat long-range dispersions allows the right understanding of vdW interactions that rule the chemical bonding within the crystal structure and that they can fully described by topological study. − …”

Section: Resultsmentioning

confidence: 99%

Crystal Structure Evolution of Fluorine under High Pressure

2022

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“…From 0 to 15 GPa we have analyzed the Laplacian of electron density within Bader’s theory to evaluate the initial Si hybridization. ,,− We searched the CPs − of function L = −∇ 2 ρ in the valence shell charge concentration to determine the atomic hybridization based on electron density distribution. Subsequently, we performed the same analysis at high pressure, only for the flat layers, to verify the achievement of ideal sp 2 hybridization of Si with pressure.…”

Section: Methods and Computational Detailsmentioning

confidence: 99%

Computational Modeling of 2D Materials under High Pressure and Their Chemical Bonding: Silicene as Possible Field-Effect Transistor

Tantardini

Kvashnin

Gatti³

et al. 2021

ACS Nano

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To study the possibility for silicene to be employed as a field-effect transistor (FET) pressure sensor, we explore the chemistry of monolayer and multilayered silicene focusing on the change in hybridization under pressure. Ab initio computations show that the effect of pressure depends greatly on the thickness of the silicene film, but also reveals the influence of real experimental conditions, where the pressure is not hydrostatic. For this purpose, we introduce anisotropic strain states. With pure uniaxial stress applied to silicene layers, a path for sp3 silicon to sp3d silicon is found, unlike with pure hydrostatic pressure. Even with mixed-mode stress (in-plane pressure half of the out-of-plane one), we find no such path. In addition to introducing our theoretical approach to study 2D materials, we show how the hybridization change of silicene under pressure makes it a good FET pressure sensor.

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“…Previous works have suggested the S–O bond in similar molecules to be more complex than previously believed. , Thus, obtaining a complete understanding of the sulfonamide electronic structure in pharmaceutical molecules is crucial. This work employs a detailed topological analysis of the S–O bonding structure present in piroxicam [PXM; Figure ], through the framework of Bader’s quantum theory of atoms in molecules (QTAIM). − In recent years, a related topological tool, the source function (SF), was shown to give a feasible description of subtle electron-delocalization effects that determinate the molecular and crystal properties − and recently was also extended to plane waves (PW) to study periodic systems . Its combination with traditional QTAIM analysis offers unique means to clarify the electronic structure of sulfonamide.…”

Section: Introductionmentioning

confidence: 99%

“…38−40 In recent years, a related topological tool, the source function (SF), was shown to give a feasible description of subtle electron-delocalization effects that determinate the molecular and crystal properties 41−51 and recently was also extended to plane waves (PW) to study periodic systems. 52 Its combination with traditional QTAIM analysis offers unique means to clarify the electronic structure of sulfonamide.…”

Section: ■ Introductionmentioning

confidence: 99%

Hypervalency in Organic Crystals: A Case Study of the Oxicam Sulfonamide Group

2016

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The theoretical charge density of the active pharmaceutical ingredient piroxicam (PXM) was evaluated through density functional theory with a localized basis set. To understand the electronic nature of the sulfur atom within the sulfonamide group, a highly ubiquitous functional group in pharmaceutical molecules, a theoretical charge density study was performed on PXM within the framework of Bader theory. Focus is on developing a topological description of the sulfur atom and its bonds within the sulfonamide group. It was found that sulfur d-orbitals do not participate in bonding. Instead, the existence of a strongly polarized ("ionic") bonding structure is found through a combined topological and natural bonding orbital analysis. This finding is in stark contrast to long-held theories of the bonding structure of organic sulfonamide and has important implications for the parametrization of calculations using classical approaches.

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Source function and plane waves: Toward complete bader analysis

Cited by 8 publications

References 52 publications

Crystal Structure Evolution of Fluorine under High Pressure

Crystal Structure Evolution of Fluorine under High Pressure

Computational Modeling of 2D Materials under High Pressure and Their Chemical Bonding: Silicene as Possible Field-Effect Transistor

Hypervalency in Organic Crystals: A Case Study of the Oxicam Sulfonamide Group

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