Interactions of a Mn atom with halogen atoms and stability of its half-filled 3d-shell

Kalpataru Pradhan; Gennady L Gutsev; Charles A Weatherford; Purusottam Jena

doi:10.1063/1.3601753

Interactions of a Mn atom with halogen atoms and stability of its half-filled 3d-shell

J Chem Phys. 2011 Jun 21;134(23):234311. doi: 10.1063/1.3601753.

Authors

Kalpataru Pradhan¹, Gennady L Gutsev, Charles A Weatherford, Purusottam Jena

Affiliation

¹ Physics Department, Virginia Commonwealth University, Richmond, Virginia 23284, USA.

PMID: 21702560
DOI: 10.1063/1.3601753

Abstract

Using density functional theory with hybrid exchange-correlation potential, we have calculated the geometrical and electronic structure, relative stability, and electron affinities of MnX(n) compounds (n = 1-6) formed by a Mn atom and halogen atoms X = F, Cl, and Br. Our objective is to examine the extent to which the Mn-X interactions are similar and to elucidate if/how the half-filled 3d-shell of a Mn atom participates in chemical bonding as the number of halogen atoms increases. While the highest oxidation number of the Mn atom in fluorides is considered to be +4, the maximum number of halogen atoms that can be chemically attached in the MnX(n)(-) anions is 6 for X = F, 5 for X = Cl, and 4 for X = Br. The MnCl(n) and MnBr(n) neutrals are superhalogens for n ≥ 3, while the superhalogen behavior of MnF(n) begins with n = 4. These results are explained to be due to the way different halogen atoms interact with the 3d electrons of Mn atom.