ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Infrared spectra of I−⋅(CH3OH)n⋅Arm, n=1,2 clusters, obtained via argon and methanol predissociation, are interpreted with the aid of ab initio calculations of the OH stretching fundamentals. The spectra of the cold, argon-solvated clusters establish the coexistence of two isomeric forms of the n=2 cluster, with the asymmetric isomer displaying a dramatic (∼150 cm−1) OH red-shift relative to both the symmetric isomer and the n=1 complex. We trace this red-shift to cooperative H-bonding which is only operative in the asymmetric form. At the higher internal energies afforded by the bare (i.e., Ar-free) complexes, the spectra are radically changed. The strongly red-shifted band is suppressed, reflecting the loss of the cooperative effect as the methanol molecules are separated, while the bands assigned to the more open form are enhanced. © 2002 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1451249
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