Premium
Group 12 Dihalides: Structural Predilections from Gases to Solids
Author(s) -
Donald Kelling J.,
Hargittai Magdolna,
Hoffmann Roald
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200801035
Subject(s) - chemistry , group (periodic table) , crystal structure , monomer , crystallography , molecule , molecular symmetry , bond length , main group element , density functional theory , zinc , computational chemistry , transition metal , organic chemistry , polymer , catalysis
Connections between the structures of Group 12 dihalides in their vapor and crystal phases are sought and discussed. The molecular structures of all monomers and dimers (MX 2 : M=Zn, Cd, Hg and X=F, Cl, Br, I) were calculated at the density functional B3PW91 and MP2 computational levels. All the monomers are linear, with the mercury dihalide molecules having shorter bonds than their cadmium analogues; the ZnX 2 and CdX 2 structures are similar. The shorter HgX distances are traced back to relativistic effects. For the dimers, many possible geometrical arrangements were considered. The zinc and cadmium dihalide dimers have the usual D 2 h ‐symmetry geometry, whereas the mercury dihalide dimers are loosely‐bound units with C 2 h symmetry. The origins of this C 2 h structure are discussed from different points of view, including frontier orbital interactions. The crystals of Group 12 dihalides span a wide range of structure types, from three‐dimensional extended solids to molecular crystals. There is an obvious connection between the structures and characteristics of monomers, their dimers, and the crystals they form. The similarities as well as startling differences from the Group 2 dihalides are analyzed.