Structures and vibrational spectra of phenol-(acetylene)n (Ph(Ac)n) 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)n (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−1 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)n (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)n clusters lying in a narrow energy range is found to be responsible for the broadening and weakening of the O-H band.
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