High Valent Mercury Fluoride Ions

Mercury poly fluoride ions (HgF_n ^±) are noted in the laser ablation of HgF_2(s) by the time-of-flight mass spectrometry. The formation of HgF_n=3,4 ^±,_6-8 ⁻ indicates the existence of corresponding precursor molecules that signify the remarkable participation of 5d Hg electrons in the chemical bonding with F atoms similar to other transition metals.

Abstract

Mercury fluoride ions formed during the laser ablation of HgF_2(s) show the formation of six different cluster ion series viz., HgF_n ^±, Hg_nF_n–2 ^±, Hg_nF_n–1 ^±, (HgF)_n ^±, Hg_nF_n+1 ^±, and Hg_nF_n+2 ^±. Among the different ion series, the observation of high valent HgF_n ^± _(n ^± _{=3,4; n} ⁻ _=6–8) indicates the existence of corresponding molecules which signify the remarkable participation of 5d Hg electrons in the chemical bonding with F atoms and thus make Hg a truly transition metal. Further, molecular orbital calculations show a large HOMO-LUMO energy gap (≥3 eV) and high electron affinity (≥5 eV) that indicates highly stable HgF_n=3,4,6,8 with super halogen properties.

Zum Volltext