Proton Defect Solvation and Dynamics in Aqueous Acid and Base

Kale, Seyit; Herzfeld, Judith

doi:10.1002/anie.201203568

Cited by 31 publications

(50 citation statements)

References 38 publications

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“…Optimism regarding kernel-kernel potentials is supported by the effectiveness of the kernel-kernel potentials developed in the earlier LEWIS model of water [28,29] which allowed for an excellent description of the solvation and dynamics of proton defects in bulk water [30]. Limitations of that construct were its modelling of the valence electrons in pairs with a fixed cloud radius.…”

Section: Resultsmentioning

confidence: 99%

Pointillist rendering of electron charge and spin density suffices to replicate trends in atomic properties

Ekesan¹,

Herzfeld²

2015

Proc. R. Soc. A.

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The monotonic and non-monotonic variations of atomic properties within and between the rows of the periodic table underlie our understanding of chemistry and accounting for these variations has been a signature strength of quantum mechanics (QM). However, the computational burden of QM motivates the development of more efficient means of describing electrons and reactivity. The recently developed LEWIS • model incorporates lessons learnt from QM into a force field that includes electrons as explicit pseudo-classical particles. Here, we extend LEWIS • across the 2p and 3p elements, and show that it is capable of reproducing both monotonic and non-monotonic variations of chemically important atomic properties in a cost-effective manner. An indicator of the strength of the construct is the ability of pairwise potentials trained on ionization energies and the order of spin configurations to predict atomic polarizabilities. In this manner, some insights of QM are uncoupled from its onerous computational burden.

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Section: Resultsmentioning

confidence: 99%

Pointillist rendering of electron charge and spin density suffices to replicate trends in atomic properties

Ekesan¹,

Herzfeld²

2015

Proc. R. Soc. A.

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“…The LEWIS force field takes this tack and also simplifies the problem by making only the valence electrons explicit and modeling them in pairs. For water, LEWIS provides an excellent description of cluster structures, the condensed phase, and proton defect solvation and dynamics . In the last case, it offered a new perspective on discrepancies in results obtained with different approximations of density functional theory (DFT).…”

Section: Introductionmentioning

confidence: 99%

Transferable pseudoclassical electrons for aufbau of atomic ions

2014

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Generalizing the LEWIS reactive force field from electron pairs to single electrons, we present LEWIS• in which explicit valence electrons interact with each other and with nuclear cores via pairwise interactions. The valence electrons are independently mobile particles, following classical equations of motion according to potentials modified from Coulombic as required to capture quantum characteristics. As proof of principle, the aufbau of atomic ions is described for diverse main group elements from the first three rows of the periodic table, using a single potential for interactions between electrons of like spin and another for electrons of unlike spin. The electrons of each spin are found to distribute themselves in a fashion akin to the major lobes of the hybrid atomic orbitals, suggesting a pointillist description of the electron density. The broader validity of the LEWIS• force field is illustrated by predicting the vibrational frequencies of diatomic and triatomic hydrogen species.

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“…4,14 The importance of getting the molecular polarizability right has been underscored by a recent comparison between MP2 and DFT/GGA results. 15 As shown in Fig.…”

Section: Lewis Simulations Of the Acid–base Behavior Of Watermentioning

confidence: 99%