Transferable pseudoclassical electrons for aufbau of atomic ions

Ekesan, Şölen; Kale, Seyit; Herzfeld, Judith

doi:10.1002/jcc.23612

Cited by 16 publications

(29 citation statements)

References 28 publications

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“…It could be interesting to try using those optimal positions as FOD starting guesses. Such force fields exist, for example in the form of the LEWIS or the LEWIS • force fields . Unfortunately, these force fields are limited to only a few chemical elements, and there is no free implementation available.…”

Section: Fermi‐orbital Descriptor Generatorsmentioning

confidence: 99%

Interpretation and Automatic Generation of Fermi‐Orbital Descriptors

et al. 2019

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We present an interpretation of Fermi‐orbital descriptors (FODs) and argue that these descriptors carry chemical bonding information. We show that a bond order derived from these FODs agrees well with reference values, and highlight that optimized FOD positions used within the Fermi‐Löwdin orbital self‐interaction correction (FLO‐SIC) method correspond to expectations from Linnett's double‐quartet theory, which is an extension of Lewis theory. This observation is independent of the underlying exchange‐correlation functional, which is shown using the local spin density approximation, the Perdew–Burke–Ernzerhof generalized gradient approximation (GGA), and the strongly constrained and appropriately normed meta‐GGA. To make FOD positions generally accessible, we propose and discuss four independent methods for the generation of Fermi‐orbital descriptors, their implementation as well as their advantages and drawbacks. In particular, we introduce a re‐implementation of the electron force field, an approach based on the centers of mass of orbital densities, a Monte Carlo‐based algorithm, and a method based on Lewis‐like bonding information. All results are summarized with respect to future developments of FLO‐SIC and related methods. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.

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Section: Fermi‐orbital Descriptor Generatorsmentioning

confidence: 99%

Interpretation and Automatic Generation of Fermi‐Orbital Descriptors

et al. 2019

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“…All are coulombic at long distances, to conform to classical electrostatics, and finite at short distances on account of the diffuse distribution of the electrons [12]. Of course, numerous functions have these features and, as for the functionals in DFT, the quality of a given set of potentials must be evaluated empirically.…”

Section: (B) Interactions and Potential Formsmentioning

confidence: 99%

“…The interactions between the particles are strictly pairwise to maximize efficiency, and smoothly differentiable to ensure energy conservation in simulations. All are coulombic at long distances, to conform to classical electrostatics, and finite at short distances on account of the diffuse distribution of the electrons [12]. Of course, numerous functions have these features and, as for the functionals in DFT, the quality of a given set of potentials must be evaluated empirically.…”

Section: (B) Interactions and Potential Formsmentioning

confidence: 99%

“…Recently, we developed potentials for repulsions between pseudo-particles representing like-spin and unlike-spin electrons. After designing them on the basis of data for two elements, we then showed that they could also describe aufbau for three other elements scattered among the first three rows of the periodic table [12]. As the next step, we now wish to fill in the gaps in order to explore the potential for describing trends in periodic properties.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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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“…The usefulness of electron pairs as the basis of the representation lies on the fact that paired electrons behave very much like bosons. 4,5 This means that Pauli correlation is minimized in a system composed by perfectly localized electron pairs, so that the exchangecorrelation term (more difficult to disentangle with simple models) is minimal. These advantages have been exploited in both, classical approaches, such as the Bond Charge Model (BCM), 6,7 where only potential and kinetic energy terms are included; as well as in more updated formulations based on quantum mechanical calculations.…”

Section: Introductionmentioning

confidence: 99%