Graphitic Phase of NaCl. Bulk Properties and Nanoscale Stability

J Phys Chem Lett. 2014 Nov 20;5(22):4014-9. doi: 10.1021/jz502046f. Epub 2014 Nov 5.

Abstract

We applied the ab initio approach to evaluate the stability and physical properties of the nanometer-thickness NaCl layered films and found that the rock salt films with a (111) surface become unstable with thickness below 1 nm and spontaneously split to graphitic-like films for reducing the electrostatic energy penalty. The observed sodium chloride graphitic phase displays an uncommon atomic arrangement and exists only as nanometer-thin quasi-two-dimensional films. The graphitic bulk counterpart is unstable and transforms to another hexagonal wurtzite NaCl phase that locates in the negative-pressure region of the phase diagram. It was found that the layers in the graphitic NaCl film are weakly bounded with each other with a binding energy order of 0.1 eV per stoichiometry unit. The electronic band gap of the graphitic NaCl displays an unusual nonmonotonic quantum confinement response.

Keywords: dipole; nanometer thick films; phase transition; sodium chloride; two-dimensional materials.