A Perspective on the So‐Called Dual Descriptor

Guégan, Frédéric; Merzoud, Lynda; Chermette, Henry; Morell, Christophe

doi:10.1002/9781119683353.ch6

Cited by 3 publications

(2 citation statements)

References 34 publications

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“…These computations were performed using the resolution of identity technique as implemented in the TURBOMOLE program. 66 In the framework of conceptual density functional theory, 67 maximal interactions with a nucleophile (respectively an electrophile) is expected when the quantity:Δ f ( r ) = f ( r ) + − f ( r ) − is maximal (respectively minimal). Δ f is the so-called dual descriptor, and f + and f − are, respectively, the electrophilic and nucleophilic Fukui functions: f ( r ) + = ρ N +1 ( r ) − ρ N ( r ) f ( r ) − = ρ N ( r ) − ρ N −1 ( r )where ρ N , ρ N +1 and ρ N −1 represent the electron density of the neutral species ( N electrons) and of the corresponding anion ( N + 1 electrons) and cation ( N − 1 electrons) at the geometry of the neutral species.…”

Section: Methodsmentioning

confidence: 99%

Section: Molecular Modellingmentioning

confidence: 99%

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In vivo stability of ²¹¹At-radiopharmaceuticals: on the impact of halogen bond formation

Yssartier,

Liu,

Pardoue

et al. 2024

RSC Med. Chem.

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Section: Methodsmentioning

confidence: 99%

Section: Molecular Modellingmentioning

confidence: 99%

In vivo stability of ²¹¹At-radiopharmaceuticals: on the impact of halogen bond formation

Yssartier,

Liu,

Pardoue

et al. 2024

RSC Med. Chem.

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Exploring chemical reactivity through a combined conceptual DFT and ELF topology approach

Courbière,

Pilmé

2024

J Mol Model

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Evaluating the Chemical Reactivity of DFT-Simulated Liquid Water with Hydrated Electrons via the Dual Descriptor

Borrelli,

Liu,

Schwartz

2024

J. Chem. Theory Comput.

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Modeling the various properties of liquid water, particularly its reactivity, has been a longstanding challenge for simulation methods. Recently, ab initio simulations based on density functional theory (DFT) have come to the fore as tenable methods for calculating the properties and reactivity of water, with varying degrees of success for different exchange-correlation functionals. In particular, hybrid-GGA and meta-GGA functionals have been shown to reproduce many of the structural, dynamical, and energetic properties of water to a high degree of accuracy relative to their computational cost. Here, we show that the dual descriptor (DD) measure of nucleophilicity and electrophilicity, which is sometimes used to elucidate organic chemistry reaction mechanisms, can also be used to characterize the reactivity of DFTsimulated liquid water. The DD is especially apt for understanding the reactivity of excess electrons with water as its calculation explicitly involves adding and removing an excess electron from a reference system. We use the DD to explore the reactivity of water simulated using three different DFT functionals: the LDA functional (LDA), a hybrid-GGA functional (PBE0), and a hybrid meta-GGA functional (SCAN0). Using the DD, we show that the SCAN0 functional with the standard 25% Hartree−Fock exchange produces simulated liquid water with many regions that are far more reactive than either PBE0 or LDA. To understand the implications of these highly reactive regions, we then add a strong nucleophile in the form of an excess electron and find that although PBE0 and LDA predict stable hydrated electrons, the excess electron reacts nearly instantaneously with SCAN0 water via proton abstraction to form a hydrogen atom and hydroxide ion. We show that the DD provides the ability to not only predict whether or not liquid water will react with a hydrated electron but also which particular waters will be involved solely from analyzing pure water configurations generated with each functional. We rationalize this result in terms of the known trap-seeking behavior of injected hydrated electrons, which are able to find the most electronegative region in bulk water. These results highlight the utility of the dual descriptor as a fast and interpretable method for investigating condensed-phase reactivity with excess electrons.

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A Perspective on the So‐Called Dual Descriptor

Cited by 3 publications

References 34 publications

In vivo stability of ²¹¹At-radiopharmaceuticals: on the impact of halogen bond formation

In vivo stability of ²¹¹At-radiopharmaceuticals: on the impact of halogen bond formation

Exploring chemical reactivity through a combined conceptual DFT and ELF topology approach

Evaluating the Chemical Reactivity of DFT-Simulated Liquid Water with Hydrated Electrons via the Dual Descriptor

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A Perspective on the So‐Called Dual Descriptor

Cited by 3 publications

References 34 publications

In vivo stability of 211At-radiopharmaceuticals: on the impact of halogen bond formation

In vivo stability of 211At-radiopharmaceuticals: on the impact of halogen bond formation

Exploring chemical reactivity through a combined conceptual DFT and ELF topology approach

Evaluating the Chemical Reactivity of DFT-Simulated Liquid Water with Hydrated Electrons via the Dual Descriptor

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Product

Resources

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In vivo stability of ²¹¹At-radiopharmaceuticals: on the impact of halogen bond formation

In vivo stability of ²¹¹At-radiopharmaceuticals: on the impact of halogen bond formation