Cooperativity in Alcohol–Nitrogen Complexes:
Understanding Cryomatrices through Slit Jet Expansions
Version 2 2017-05-23, 04:29
Version 1 2017-04-26, 14:03
Posted on 2017-05-23 - 04:29
FTIR spectroscopy of supersonic expansions
is used to characterize
alcohol dimers with one, two, and several nitrogen molecules attached
to them. The nitrogen coating causes progressive spectral downshifts
of the OH stretching fundamentals which are related to and explain
matrix isolation shifts. Comparison of methanol, tert-butyl alcohol and ethanol as well as deuteration of methanol assist
in the assignment. Alcohol monomers and trimers are significantly
more resistant to nitrogen coating due to a lack of cooperativity
and dangling bonds, respectively. In the case of ethanol, the role
of conformational isomerism and combination bands is further elucidated.
The experimental findings help rationalize the anomalously small OH
stretching dimerization shift of methanol in the gas phase, in comparison
to that of tert-butyl alcohol.
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Oswald, Sönke; Wallrabe, Mareike; Suhm, Martin A. (2017). Cooperativity in Alcohol–Nitrogen Complexes:
Understanding Cryomatrices through Slit Jet Expansions. ACS Publications. Collection. https://doi.org/10.1021/acs.jpca.7b01265
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AUTHORS (3)
SO
Sönke Oswald
MW
Mareike Wallrabe
MS
Martin A. Suhm