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Binary Complexes of Ammonia with Phenylacetylenes: A Combined Experimental and Computational Approach to Explore Multiple Minima on Intermolecular Potentials

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Title Binary Complexes of Ammonia with Phenylacetylenes: A Combined Experimental and Computational Approach to Explore Multiple Minima on Intermolecular Potentials
 
Creator DEY, A
MONDAL, SI
PATWARI, GN
 
Subject ab initio calculations
ammonia
hydrogen bonds
phenylacetylene
substituent effect
DOUBLE-RESONANCE SPECTROSCOPY
ULTRAVIOLET DOUBLE-RESONANCE
HYDROGEN-BONDED COMPLEXES
WATER
ENERGIES
 
Description The hydrogen-bonded complexes of phenylacetylene, 4-fluorophenylacetylene, 2-fluorophenylacetylene, and 2,6-difluorophenylacetylene with ammonia are investigated using IRUV double resonance spectroscopy in combination with high-level ab initio calculations at the CCSD(T)/CBS level of theory. The CHN hydrogen-bonded complex, which involves an interaction of ammonia with the acetylenic CH group is the global minimum and is observed in all four cases investigated. In addition, phenylacetylene and 4-fluorophenylacetylene form a quasi-planar cyclic complexes with ammonia incorporating NH and CHN hydrogen bonds, wherein the -electron density of the acetylenic CC bond acts as an acceptor to the NH group of ammonia. A third ammonia complex is observed for 4-fluorophenylacetylene in which ammonia interacts with the fluorine atom once again, leading to the formation of a quasi-planar cyclic complex. The substitution of the fluorine atom on the phenyl ring of phenylacetylene modulates the intermolecular potentials, which are dependent on the position of the substitution.
 
Publisher WILEY-V C H VERLAG GMBH
 
Date 2014-10-16T14:36:45Z
2014-10-16T14:36:45Z
2013
 
Type Article
 
Identifier CHEMPHYSCHEM, 14(4)746-753
http://dx.doi.org/10.1002/cphc.201200797
http://dspace.library.iitb.ac.in/jspui/handle/100/15801
 
Language en