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  The elusive ≡C-H⋯O complex in the hydrogen bonded systems of Phenylacetylene: A Matrix Isolation Infrared and Ab Initio Study

Karir, G., Fatima, M., & Viswanathan, K. S. (2016). The elusive ≡C-H⋯O complex in the hydrogen bonded systems of Phenylacetylene: A Matrix Isolation Infrared and Ab Initio Study. Journal of Chemical Sciences, 128(10), 1557-1569. doi:10.1007/s12039-016-1166-1.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002B-B90B-F Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002B-B90C-D
Genre: Journal Article

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http://dx.doi.org/10.1007/s12039-016-1166-1 (Publisher version)
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 Creators:
Karir, Ginny1, Author
Fatima, Mariyam1, 2, 3, Author              
Viswanathan, K. S.1, Author
Affiliations:
1Department of Chemical Sciences, Indian Institute of Science Education and Research, Sector 81, Mohali, Punjab, 140 306 India, ou_persistent22              
2Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_1938292              
3International Max Planck Research School for Ultrafast Imaging & Structural Dynamics (IMPRS-UFAST), Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_2266714              

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Free keywords: Methanol; hydrogen bonded systems; Diethyl ether; ab initio computations; matrix isolation; infrared spectroscopy
 Abstract: Hydrogen-bonded complexes of phenylacetylene (PhAc) with methanol (MeOH) and diethylether (DEE) were studied using matrix isolation infrared spectroscopy. This study specifically searched for the ≡C-H⋯O hydrogen bonded complex in these systems, which manifest a n-σ* interaction and which is a local minimum on the PhAc-MeOH potential surface, as in the case of PhAc-H2O heterodimer. This n-σ* local minimum eluded observation in gas phase studies and it was therefore thought interesting to look for this isomer in cryogenic matrices. While MeOH can interact with PhAc as both a proton donor (O-H⋯π complex) or a proton acceptor (n-σ* complex), DEE can only manifest the n-σ* isomer. A comparison of the spectral shifts observed in the features of PhAc-MeOH and PhAc-DEE would therefore independently confirm the existence or not of n-σ* complex in both these systems. In addition to the n-σ* complex observed in both the above systems, the O-H⋯π complex was also discerned in the PhAc-MeOH system. These complexes have stabilization energy in the range of 8-25 kJ /mol. The experimental results were corroborated by computations performed at MP2 and M06-2X, levels of theory, using 6-311++G(d,p) and aug-cc-pVDZ basis sets. Single point calculations at the CCSD level of theory were also performed. Atoms-in-molecules (AIM), NBO and LMOEDA analysis were also performed to understand the nature of the intermolecular interactions in these complexes.

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Language(s): eng - English
 Dates: 2016-08-192016-08-012016-08-192016-09-282016-10
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1007/s12039-016-1166-1
 Degree: -

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Title: Journal of Chemical Sciences
  Abbreviation : J. Chem. Sci.
Source Genre: Journal
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Publ. Info: Bangalore, India : Indian Academy of Sciences
Pages: - Volume / Issue: 128 (10) Sequence Number: - Start / End Page: 1557 - 1569 Identifier: ISSN: 0974-3626
CoNE: https://pure.mpg.de/cone/journals/resource/0974-3626