Theoretical study of lithium clusters by electronic stress tensor

TL;DR

This study investigates the electronic stress tensor in lithium clusters, revealing that their eigenvalues are negative and degenerate, which may serve as indicators of metallic bonding characteristics.

Contribution

It proposes a novel approach to characterize metallic bonds using the electronic stress tensor and introduces indices to distinguish metallicity from covalency.

Findings

Eigenvalues of Li clusters' stress tensor are negative and degenerate.

Degeneracy and sign of eigenvalues can differentiate metallic from covalent bonds.

Differential eigenvalues serve as potential indices for metallicity evaluation.

Abstract

We study the electronic structure of small lithium clusters Li_n (n=2-8) using the electronic stress tensor. We find that the three eigenvalues of the electronic stress tensor of the Li clusters are negative and degenerate, just like the stress tensor of liquid. This leads us to propose that we may characterize a metallic bond in terms of the electronic stress tensor. Our proposal is that in addition to the negativity of the three eigenvalues of the electronic stress tensor, their degeneracy characterizes some aspects of the metallic nature of chemical bonding. To quantify the degree of degeneracy, we use the differential eigenvalues of the electronic stress tensor. By comparing the Li clusters and hydrocarbon molecules, we show that the sign of the largest eigenvalue and the differential eigenvalues could be useful indices to evaluate the metallicity or covalency of a chemical bond.