Document Type

Article

Publication Date

2021

DOI

10.1063/5.0066626

Publication Title

The Journal of Chemical Physics

Volume

155

Issue

21

Pages

1-14

Abstract

Atoms remaining as recognizably distinct constituents of bulk condensed phases can have properties modified from those of the isolated species. Dense helium bubbles at high pressures are a common form of radiation damage degrading the mechanical and electrical properties of host materials. Detailed knowledge is critical for predicting their long term performance. Modifications of the ground and first singlet excited states of confined compressed helium are investigated using an entirely non-empirical theory based on the results of ab initio self-consistent field calculations with corrections for the effects of electron correlation. For finite sized portions representing bulk condensed fcc and bcc phases of helium atoms, Hartree–Fock wavefunctions, energies, and charge distributions were computed as a function of different atomic densities using two models. The first model for the first excited state localizes the excitation on the central atom; in the second model, this is partially delocalized over the closest atomic neighbors. Total energies for the finite size portions are derived by adding the inter-atomic dispersive attractions and a density functional description of the short-range inter-atomic correlation energy. The experimental energy of the first allowed electronic transition increases with density being larger than in an isolated atom. The intra-atomic correlation energy does not contribute to this energy shift. The calculated energy shifts agree well with experiment for both bulk solid and liquid helium. The 2p orbital is increasingly compressed by density enhancement, thus generating the energy shifts. Consequently, calculations of the inelastic electron scattering cross sections are substantially incorrect if the compression of the final 1s2p state is not included. The character of the excitations is examined, and it is argued that these are of Frenkel rather than the Wannier type.

Comments

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP publishing. This article appeared in The Journal of Chemical Physics, Volume 155, Issue 21, Article number 214301 and may be found at: https://doi.org/10.1063/5.0066626.

Included after a 12 month embargo in compliance with publisher policies.

Original Publication Citation

Pyper, N. C., Naginey, T. C., & Whelan, C. T. (2021). Environmental modifications of atomic properties: The ground and 1s2p excited states of compressed helium. The Journal of Chemical Physics, 155(21), 1-14, Article 214301. https://doi.org/10.1063/5.0066626

ORCID

0000-0002-3816-2799 (Whelan)

Available for download on Thursday, December 01, 2022

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