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The interactions of FeBr 2 , CoBr 2 , NiBr 2 , and ZnBr 2 with Ne, Ar, Kr, Xe, CH 4 , and N 2 matrices have been investigated using IR, electronic absorption, and X-ray absorption spectroscopies as well as DFT calculations. ZnBr 2 is linear in all of the matrices. NiBr 2 is linear in all but N 2 matrices, where it is severely bent. For FeBr 2 and CoBr 2 here is a more gradual change, with evidence of nonlinearity in Xe and CH 4 matrices as well as N 2 . In the N 2 matrices, the presence of ν NN modes blue-shifted from the "free" N 2 values indicates the presence of physisorbed species, and the magnitude of the blue shift correlates with the shift in the ν 3 mode of the metal dibromide. In the case of NiCl 2 and NiBr 2 , chemisorbed species are formed after photolysis, but only if deposition takes place below 10 K. There was no evidence for chemisorbed species for NiF 2 and FeBr 2 , and in the case of CoBr 2 he evidence was not strong.

the journal of physical chemistry a

How Inert, Perturbing, or Interacting Are Cryogenic Matrices? A Combined Spectroscopic (Infrared, Electronic, and X-ray Absorption) and DFT Investigation of Matrix-Isolated Iron, Cobalt, Nickel, and Zinc Dibromides