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A Combined Spectroscopic and ab Initio Investigation of Phenylacetylene-Methylamine Complex. Observation of sigma and pi Type Hydrogen-Bonded Configurations and Fluorescence Quenching by Weak C-H center dot center dot center dot N Hydrogen Bonding

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Title A Combined Spectroscopic and ab Initio Investigation of Phenylacetylene-Methylamine Complex. Observation of sigma and pi Type Hydrogen-Bonded Configurations and Fluorescence Quenching by Weak C-H center dot center dot center dot N Hydrogen Bonding
 
Creator MAITY, S
DEY, A
PATWARI, GN
KARTHIKEYAN, S
KIM, KS
 
Subject ultraviolet double-resonance
stretching vibrations
molecular clusters
benzene dimer
water
energies
systems
design
origin
amines
 
Description Two distinct isomers for the binary complex between phenylacetylene and methylamine were observed. The first complex is characterized by the presence of a C-H center dot center dot center dot N hydrogen bond between the acetylenic C-H group and the N atom of methylamine. In the second complex the N-H group of methylamine interacts with the pi electron density of the benzene ring accompanied by a peripheral interaction between the methyl C-H group and the pi electron density of the C C bond. Stabilization energies and Gibbs free energies at the complete basis set (CBS) limit of the coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)] suggest that while the C-H center dot center dot center dot N hydrogen bonded complex is the global minimum, the N-H center dot center dot center dot pi hydrogen bonded complex is a high energy local minimum. The formation of the N-H center dot center dot center dot pi complex could be related to kinetic trapping or higher accessibility. Comparison of the laser induced fluorescence (LIF) excitation and the one-color-resonant two-photon ionization (1C-R2PI) spectra suggests that formation of C-H center dot center dot center dot N hydrogen bonding leads to fluorescence quenching in phenylacetylene, most probably due to dipolar coupling in the excited state. The binary complex between the phenylacetylene and methylamine shows interesting isomer-dependent fluorescent properties.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-07-13T13:18:31Z
2011-12-26T12:47:53Z
2011-12-27T05:41:29Z
2011-07-13T13:18:31Z
2011-12-26T12:47:53Z
2011-12-27T05:41:29Z
2010
 
Type Article
 
Identifier JOURNAL OF PHYSICAL CHEMISTRY A, 114(42), 11347-11352
1089-5639
http://dx.doi.org/10.1021/jp105439y
http://dspace.library.iitb.ac.in/xmlui/handle/10054/3681
http://hdl.handle.net/10054/3681
 
Language en