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A combined theoretical and experimental study of phenol-(acetylene) n (n ≤ 7) clusters.
- Source :
-
The Journal of chemical physics [J Chem Phys] 2017 Apr 21; Vol. 146 (15), pp. 154303. - Publication Year :
- 2017
-
Abstract
- Structures and vibrational spectra of phenol-(acetylene) <subscript>n</subscript> (Ph(Ac) <subscript>n</subscript> ) clusters are studied by a combination of theoretical calculations and infrared (IR) spectroscopy. The molecular electrostatic potential features are utilized for generating trial geometries of the medium-sized Ph(Ac) <subscript>n</subscript> (n = 1, 2, 4, 6, and 7) clusters. These initial geometries are subjected to geometry optimization within the second-order Møller-Plesset (MP2) theory, employing correlation consistent aug-cc-pVDZ (aVDZ) basis set. Minimal nature of the reported structures is confirmed by doing vibrational frequency run at MP2/aVDZ level of theory using full calculations for n = 1 and 2 and employing grafting based molecular tailoring approach for the n = 4, 6, and 7. Several isomers for n ≥ 4 are found to lie in an energy window of 1 kcal mol <superscript>-1</superscript> of each other. Considering the formidability of MP2 level investigation for the large number of isomers for n = 6 and 7, B97-D level theory is used for studying their energetics and IR spectra. It is seen that the number of energetically close isomers increases with increasing n. Moderately size-selected IR spectra of Ph(Ac) <subscript>n</subscript> (n = 4 and 7), prepared by a supersonic jet expansion, are measured for the acetylenic C-H and phenolic O-H stretch regions by infrared-ultraviolet (IR-UV) double resonance spectroscopy combined with time-of-flight mass spectrometry. Asymmetric line shape of the C-H stretch band and remarkable line broadening and weakening of the O-H stretch band are noteworthy features of the observed spectra. These findings of the experimental spectra are explained by the theoretical studies. The averaging of the vibrational spectrum of low-lying isomers of the Ph(Ac) <subscript>n</subscript> clusters lying in a narrow energy range is found to be responsible for the broadening and weakening of the O-H band.
Details
- Language :
- English
- ISSN :
- 1089-7690
- Volume :
- 146
- Issue :
- 15
- Database :
- MEDLINE
- Journal :
- The Journal of chemical physics
- Publication Type :
- Academic Journal
- Accession number :
- 28433025
- Full Text :
- https://doi.org/10.1063/1.4979953