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Please use this identifier to cite or link to this item: http://dspace.library.iitb.ac.in/jspui/handle/10054/3891

Title: Hydrogen-Bonded Complexes of Phenylacetylene with Water, Methanol, Ammonia, and Methylamine. The Origin of Methyl Group-Induced Hydrogen Bond Switching
Authors: SEDLAK, R
HOBZA, P
PATWARI, GN
Keywords: microwave spectroscopy
interaction energies
perturbation-theory
matrix-isolation
benzene
chemistry
dimers
model
Issue Date: 2009
Publisher: AMER CHEMICAL SOC
Citation: JOURNAL OF PHYSICAL CHEMISTRY A, 113(24), 6620-6625
Abstract: The infrared spectra in the acetylenic C-H stretching region for the complexes of phenylacetylene with water, methanol, ammonia, and methylamine are indicative of change in the intermolecular structure upon substitution with a methyl group. High-level ab initio calculations at CCSD(T)/aug-cc-pVDZ level indicate that the observed complexes of water and ammonia are energetically the most favored structures, and electrostatics play a dominant role in stabilizing these structures. The ability of the pi electron density of the benzene ring to offer a larger cross-section for the interaction and the increased polarizability of the O-H and N-H groups in methanol and methylamine favor the formation of pi hydrogen-bonded complexes, in which dispersion is the dominant force. Further, the observed phenylacetylene-methylamine complex can be tentatively assigned to a kinetically trapped higher energy structure. The observed methyl group-induced hydrogen bond switching in the phenylacetylene complexes can be attributed to the switching of the dominant interaction from electrostatic to dispersion.
URI: http://dx.doi.org/10.1021/jp900813n
http://dspace.library.iitb.ac.in/xmlui/handle/10054/3891
http://hdl.handle.net/10054/3891
ISSN: 1089-5639
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