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Journal article
Ab initio anharmonic analysis of complex vibrational spectra of phenylacetylene and fluorophenylacetylenes in the acetylenic and aromatic C-H stretching region
The Journal of chemical physics, Vol.159(10), 104302
09/14/2023
PMID: 37681698
Web of Science ID: WOS:001146188000001
Abstract
Vibrational spectra in the acetylenic and aromatic C-H stretching regions of phenylacetylene and fluorophenylacetylenes, viz., 2-fluorophenylacetylene, 3-fluorophenylacetylene, and 4-fluorophenylacetylene, were measured using the IR-UV double resonance spectroscopic method. The spectra, in both acetylenic and aromatic C-H stretching regions, were complex exhibiting multiple bands. Ab-initio anharmonic calculations with quartic potential using B97D3/6-311++G(d,p) and vibrational configuration interaction were able to capture all important spectral features in both the regions of the experimentally observed spectra for all four molecules considered in the present work. Interestingly, for phenylacetylene, the spectrum in the acetylenic C-H stretching region emerges due to anharmonic coupling of modes localized on the acetylenic moiety along with the other ring modes, which also involve displacements on the acetylenic group, which is in contrast to what has been proposed and propagated in the literature. In general, this coupling scheme is invariant to the fluorine atom substitution. For the aromatic C-H stretching region, the observed spectrum emerges due to the coupling of the C-H stretching with C-C stretching and C-H in-plane bending modes.
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- Title
- Ab initio anharmonic analysis of complex vibrational spectra of phenylacetylene and fluorophenylacetylenes in the acetylenic and aromatic C-H stretching region
- Publication Details
- The Journal of chemical physics, Vol.159(10), 104302
- Resource Type
- Journal article
- Publisher
- AIP Publishing
- Number of pages
- 7
- Grant note
- Science and Engineering Research Board of the Department of Science and Technology: CRG/2022/005470 Board of Research in Nuclear Sciences (BRNS): 58/14/18/2020 Inspire-IndiaMinistry of Science and Technology of Taiwan: MOST 107-2628-M001-002-MY4, MOST 111-2113-M-001-006, MOST 111-2113-M-001-023, MOST 111-2639-M-A49-001-ASP IAMS Junior FellowAcademia Sinica
This study is based upon work supported in part by the Science and Engineering Research Board of the Department of Science and Technology (Grant No. CRG/2022/005470) and the Board of Research in Nuclear Sciences (BRNS Grant No. 58/14/18/2020) to G.N.P. S.S. thanks Inspire-India for the research fellowship. Q.-R.H., J.A.T., and J.-L.K. are supported by various grants from the Ministry of Science and Technology of Taiwan (Grant Nos. MOST 107-2628-M001-002-MY4, MOST 111-2113-M-001-006, MOST 111-2113-M-001-023, and MOST 111-2639-M-A49-001-ASP) to J.-L.K., Q.-R.H., and J.A.T. were supported via the IAMS Junior Fellow and other grants from Academia Sinica. G.N.P. is presently on sabbatical at the Institute of Atomic and Molecular Sciences, Academia Sinica.
- Copyright
- Rights managed by AIP Publishing.
- Identifiers
- WOS:001146188000001; 99381548017206600
- Academic Unit
- Chemistry; Hal Marcus College of Science and Engineering
- Language
- English