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

Wilkin, Owen M.; Harris, Neil; Rooms, John F.; Dixon, Emma L.; Bridgeman, Adam J.; Young, Nigel A.

Abstract

The interactions of FeBr2, CoBr2, NiBr2 and ZnBr2 with Ne, Ar, Kr, Xe, CH4 and N2 matrices have been investigated using IR, electronic absorption and X-ray absorption spectroscopies, as well as DFT calculations. ZnBr2 is linear in all the matrices. NiBr2 is linear in all but N2 matrices where it is severely bent. For FeBr2 and CoBr2 there is a more gradual change, with evidence of non-linearity in Xe and CH4 matrices as well as N2. In the N2 matrices the presence of νNN modes blue shifted from the “free” N2 values indicates the presence of physisorbed species, and the magnitude of the blue-shift correlates with the shift in the ν3 mode of the metal dibromide. In the case of NiCl2 and NiBr2 chemisorbed species are formed after photolysis, but only if deposition takes place below 10 K. There was no evidence for chemisorbed species for NiF2 and FeBr2 and in the case of CoBr2 the evidence was not strong.

Citation

Wilkin, O. M., Harris, N., Rooms, J. F., Dixon, E. L., Bridgeman, A. J., & Young, N. A. (2018). 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. The journal of physical chemistry. A, 122(8), 1994-2029. https://doi.org/10.1021/acs.jpca.7b09734

• Journal Article Type: Article
• Acceptance Date: Dec 28, 2017
• Online Publication Date: Feb 19, 2018
• Publication Date: Mar 1, 2018
• Deposit Date: Mar 6, 2018
• Publicly Available Date: Oct 27, 2022
• Journal: The Journal of Physical Chemistry A
• Print ISSN: 1089-5639
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 122
• Issue: 8
• Pages: 1994-2029
• DOI: https://doi.org/10.1021/acs.jpca.7b09734
• Keywords: Physical and Theoretical Chemistry
• Public URL: https://hull-repository.worktribe.com/output/719001
• Publisher URL: https://pubs.acs.org/doi/abs/10.1021/acs.jpca.7b09734
• Contract Date: Mar 6, 2018