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Structures of HCI and HBr polymers in nitrogen matrix derived from infrared and Raman data: Comparison with argon matrix
Author(s) -
Perchard J. P.,
Maillard D.,
Schriver A.,
Girardet C.
Publication year - 1981
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.1250110520
Subject(s) - trimer , raman spectroscopy , chemistry , dimer , molecule , intermolecular force , polymer , tetramer , infrared , infrared spectroscopy , matrix (chemical analysis) , matrix isolation , chemical physics , computational chemistry , organic chemistry , physics , optics , chromatography , enzyme
The structures of HCI and HBr polymers trapped in nitrogen matrices are re‐examined at the light of new Raman data. From the comparison with IR vibrational spectra including H/D decoupling experiments, two polymers other than the dimer are identified: an assymetric cyclic trimer in which the three molecules are not equivalent, and a cyclic tetramer in which the molecules are equivalent in pairs. In the case of HCI the trimer is seen to exist with two slightly different forms below 20 K, one of them reversibly disappearing above this temperature. The differences with the results obtained in rare gas matrices are understood as occurring from a strong anisotropic solute‐matrix potential which tends to distort the highly symmetric structure of isolated aggregates. The distorsion is perhaps at the origin of the change in the derivatives of some molecular electrical properties with respect to the intermolecular stretching coordinate from rare gas to nitrogen matrices.