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
SCIE
SCOPUS
- 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
- Authors
- Maity, S; Dey, A; Patwari, GN; Karthikeyan, S; Kim, KS
- Date Issued
- 2010-10-28
- Publisher
- AMER CHEMICAL SOC
- Abstract
- 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.
- Keywords
- ULTRAVIOLET DOUBLE-RESONANCE; STRETCHING VIBRATIONS; MOLECULAR CLUSTERS; BENZENE DIMER; WATER; ENERGIES; SYSTEMS; DESIGN; ORIGIN; AMINES
- URI
- https://oasis.postech.ac.kr/handle/2014.oak/25654
- DOI
- 10.1021/JP105439Y
- ISSN
- 1089-5639
- Article Type
- Article
- Citation
- JOURNAL OF PHYSICAL CHEMISTRY A, vol. 114, no. 42, page. 11347 - 11352, 2010-10-28
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