TY - JOUR
T1 - Complexes of molecular and ionic character in the same matrix layer
T2 - Infrared studies of the Sulfuric Acid/Ammonia system
AU - Rozenberg, Mark
AU - Loewenschuss, Aharon
AU - Nielsen, Claus J.
PY - 2011/6/16
Y1 - 2011/6/16
N2 - The atmospherically important interaction products of sulfuric acid and ammonia molecules have been firstly observed by matrix isolation Fourier transform infrared spectroscopy (MIS-FTIR). Infrared spectra of solid argon matrix layers, in which both H2SO4 and NH3 molecules were entrapped as impurities, were analyzed for bands not seen in matrix layers containing either of the parent molecules alone. Results were interpreted on the basis of spectral changes, experimental conditions, and semiempirically scaled frequencies from the B3LYP/aug-cc-pVTZ and B3LYP/aug-cc-pVQZ calculations. Bands were assigned to complexes of the H 2SO4·NH3 and H2SO4 · [NH3]2 general formulas. They differ significantly: the 1:1 H2SO4·NH3 complex is a strongly hydrogen bonded complex, an analogue of the H2SO 4·H2O complex, studied previously. For the 1:2 H2SO4·[NH3]2 complex, spectral results indicate an almost complete proton transfer forming a complex of essentially the two ionic moieties HSO4- and [H 3N⋯H⋯NH3]+, an analogue of the[H2O⋯H⋯OH2]+ "Zundel ion".
AB - The atmospherically important interaction products of sulfuric acid and ammonia molecules have been firstly observed by matrix isolation Fourier transform infrared spectroscopy (MIS-FTIR). Infrared spectra of solid argon matrix layers, in which both H2SO4 and NH3 molecules were entrapped as impurities, were analyzed for bands not seen in matrix layers containing either of the parent molecules alone. Results were interpreted on the basis of spectral changes, experimental conditions, and semiempirically scaled frequencies from the B3LYP/aug-cc-pVTZ and B3LYP/aug-cc-pVQZ calculations. Bands were assigned to complexes of the H 2SO4·NH3 and H2SO4 · [NH3]2 general formulas. They differ significantly: the 1:1 H2SO4·NH3 complex is a strongly hydrogen bonded complex, an analogue of the H2SO 4·H2O complex, studied previously. For the 1:2 H2SO4·[NH3]2 complex, spectral results indicate an almost complete proton transfer forming a complex of essentially the two ionic moieties HSO4- and [H 3N⋯H⋯NH3]+, an analogue of the[H2O⋯H⋯OH2]+ "Zundel ion".
UR - http://www.scopus.com/inward/record.url?scp=79959932607&partnerID=8YFLogxK
U2 - 10.1021/jp107369r
DO - 10.1021/jp107369r
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AN - SCOPUS:79959932607
SN - 1089-5639
VL - 115
SP - 5759
EP - 5766
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 23
ER -