Variational grand-canonical electronic structure of Li+Li at ~104 K with second-order perturbation theory corrections

Shlomit Jacobi, Roi Baer*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

An ab initio variational grand-canonical electronic structure mean-field method, based on the Gibbs-Peierls-Bogoliubov minimum principle for the Gibbs free energy, is applied to the di-lithium (Li+Li) system at temperatures around T ≈ 104 K and electronic chemical potential of μ ≈ -0.1Eh. The method is an extension of the Hartree-Fock approach to finite temperatures. We first study the Li2 molecule at a frozen inter-nuclear distance of R = 3 Å as a function of temperature. The mean-field electronic structure changes smoothly as temperature increases, up to 104 K, where a sharp spontaneous spin-polarization emerges as the variational mean-field solution. Further increase in the temperature extinguishes this polarization. We analyze the mean-field behavior using a correlated single-site Hubbard model and show it arises from an attempt of the mean-field to mimic the polarization of the spin-spin correlation function of the exact solution. Next, we keep constant the temperature at 104 K and examine the electronic structure as a function of inter-nuclear distance R. At R = 3.7 Å, a crossing between two free energy states occurs: One state is "spin-unpolarized" (becomes lower in energy when R > 3.7 Å), while the other is "spin polarized". This crossing causes near-discontinuous jumps in calculated properties of the system and is associated with using the noninteracting electron character of our mean-field approach. Such problems will likely plague FT-DFT calculations as well. We use second-order perturbation theory (PT2) to study effects of electron correlation on the potential of mean force between the two colliding Li atoms. We find that PT2 correlation free energy at ~104 K is larger than at 0 K and tends to restore the spin-polarized state as the lowest free energy solution.

Original languageAmerican English
Article number1113
Pages (from-to)1-9
Number of pages9
JournalTheoretical Chemistry Accounts
Volume131
Issue number3
DOIs
StatePublished - Mar 2012

Bibliographical note

Funding Information:
We gratefully acknowledge the Israel Science Foundation for supporting this work.

Keywords

  • Atomic plasmas
  • Finite temperature density functional theory
  • High temperatures
  • Mean field approximations

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