Exclusion principle repulsion effects on the covalent bond beyond the Born–Oppenheimer approximation

Sarsa, A.; Alcaraz-Pelegrina, J. M.; Sech, C. Le

doi:10.1039/c9cp01063g

Cited by 6 publications

(7 citation statements)

References 35 publications

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“…As a result, the very nature of the chemical bond changes, and some astonishing effects can be observed. 176,177 Noble gases, for example, become reactive under pressure. [178][179][180][181][182] Although it is in many cases unclear whether the interatomic contacts involving noble gas atoms can rightly be called chemical bonds, the observed interactions between noble gases and other species suggest that the concept of the chemical bond must be overthought in the high-pressure regime.…”

Section: Electronic Effects and Chemical Bondingmentioning

confidence: 99%

Computational high‐pressure chemistry: Ab initio simulations of atoms, molecules, and extended materials in the gigapascal regime

Zeller,

Hsieh,

Dononelli

et al. 2024

WIREs Comput Mol Sci

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The field of liquid‐phase and solid‐state high‐pressure chemistry has exploded since the advent of the diamond anvil cell, an experimental technique that allows the application of pressures up to several hundred gigapascals. To complement high‐pressure experiments, a large number of computational tools have been developed. These techniques enable the simulation of chemical systems, their sizes ranging from single atoms to infinitely large crystals, under high pressure, and the calculation of the resulting structural, electronic, and spectroscopic changes. At the most fundamental level, computational methods using carefully tailored wall potentials allow the analytical calculation of energies and electronic properties of compressed atoms. Molecules and molecular clusters can be compressed either via mechanochemical approaches or via more sophisticated computational protocols using implicit or explicit solvation approaches, typically in combination with density functional theory, thus allowing the simulation of pressure‐induced chemical reactions. Crystals and other periodic systems can be routinely simulated under pressure as well, both statically and dynamically, to predict the changes of crystallographic data under pressure and high‐pressure crystal structure transitions. In this review, the theoretical foundations of the available computational tools for simulating high‐pressure chemistry are introduced and example applications demonstrating the strengths and weaknesses of each approach are discussed.This article is categorized under: Structure and Mechanism > Computational Materials Science Electronic Structure Theory > Ab Initio Electronic Structure Methods Software > Simulation Methods

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Section: Electronic Effects and Chemical Bondingmentioning

confidence: 99%

Computational high‐pressure chemistry: Ab initio simulations of atoms, molecules, and extended materials in the gigapascal regime

Zeller,

Hsieh,

Dononelli

et al. 2024

WIREs Comput Mol Sci

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“…It is interesting to visualize the NLF as it is also defined from the localization measure in Eq. (8). We first normalize the localization measure using [4,65]…”

Section: B the Nucleon Localization Function (Nlf)mentioning

confidence: 99%

“…The orbital based determination of the Pauli kinetic energy is found to be essential for gauging the accuracy of these empirical Pauli functionals [4,5]. Similarly, the identification of the contribution of Pauli repulsion in DFT calculations of intermolecular interaction energies is of current interest in chemistry [6][7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

Pauli energy contribution to nucleus-nucleus interaction

Umar,

Simenel,

Godbey

2021

Preprint

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Background: The Pauli exclusion principle plays a crucial role as a building block of many-body quantal systems comprised of fermions. It also induces a "Pauli repulsion" in the interaction between di-nuclear systems. It has been shown in [Phys. Rev. C95, 031601 (2017)] that the Pauli repulsion widens the nucleus-nucleus potential barrier, thus hindering sub-barrier fusion. Purpose: To investigate the proton and neutron contributions to the Pauli repulsion, both in the bare potential neglecting shape polarization and transfer between the reactants, as well as in the dynamical potential obtained by accounting for such dynamical rearrangements. Methods: As the basis of our study we utilize the Pauli kinetic energy (PKE) obtained by studying the nuclear localization function (NLF). Recently this approach has been generalized to incorporate all of the dynamical and time-odd terms present in the nuclear energy density functional. This approach is employed in the density constrained Hartree-Fock (DCFHF) and in the density constrained time-dependent Hartree-Fock (DC-TDHF) microscopic methods. Results: The PKE spatial distribution shows that a repulsion occurs in the neck between the nuclei when they first touch. Inside the barrier, neutrons can contribute significantly more to the Pauli repulsion in neutron-rich systems. Dynamical effects tend to lower the Pauli repulsion near the barrier. Proton and neutron dynamical contributions to the PKE significantly differ inside the barrier for asymmetric collisions, which is interpreted as an effect of multinucleon transfer. Conclusions: The PKE is shown to make a significant contribution to nuclear interaction potentials. Protons and neutrons can play very different roles in both the bare potential and in the dynamical rearrangement. Further microscopic studies are required to better understand the role of transfer and to investigate the effect of pairing and deformation.

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“…26,27 In particular, the storage and transport of hydrogen has attracted a great deal of attention due to its use as a clean source of energy, 28,29 and several theoretical and experimental works have focused on this subject under different confining situations. [30][31][32][33][34][35][36][37][38][39][40][41][42][43] The properties of confined systems have been studied using various confinement models depending on the applications considered. Some of the most frequently studied are the spherical hard wall, [44][45][46][47][48] the finite barrier, [49][50][51] the Gaussian-well potential, [52][53][54] the square-well potential 55,56 and a combination of Woods-Saxon potentials.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

An off-center endohedrally confined hydrogen molecule

Morcillo-Arencibia

Alcaraz-Pelegrina

Rubio

et al. 2022

Phys. Chem. Chem. Phys.

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Exclusion principle repulsion effects on the covalent bond beyond the Born–Oppenheimer approximation

Abstract: Electronic depletion of the covalent bond by the Pauli exclusion principle repulsion. Energies and quantum forces are calculated.

Cited by 6 publications

References 35 publications

Computational high‐pressure chemistry: Ab initio simulations of atoms, molecules, and extended materials in the gigapascal regime

Computational high‐pressure chemistry: Ab initio simulations of atoms, molecules, and extended materials in the gigapascal regime

Pauli energy contribution to nucleus-nucleus interaction

An off-center endohedrally confined hydrogen molecule

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