Noncovalent Interactions in the Gas Phase: The Anisole鈥揚henol Complex

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• 作者：Giangaetano Pietraperzia ; Massimiliano Pasquini ; Federico Mazzoni ; Giovanni Piani ; Maurizio Becucci ; Malgorzata Biczysko ; Daniel Michalski ; Julien Bloino ; Vincenzo Barone
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：September 1, 2011
• 年：2011
• 卷：115
• 期：34
• 页码：9603-9611
• 全文大小：960K
• 年卷期：v.115,no.34(September 1, 2011)
• ISSN：1520-5215

文摘

The present paper reports on an integrated spectroscopic study of the anisole鈥損henol complex in a molecular beam environment. Combining REMPI and HR-LIF spectroscopy experimental data with density functional computations (TD-M05-2X/M05-2X//N07D) and first principle spectra simulations, it was possible to locate the band origin of the S₁ 鈫?S₀ electronic transition and determine the equilibrium structure of the complex, both in the S₀ and S₁ electronic states. Experimental and computational evidence indicates that the observed band origin is due to an electronic transition localized on the phenol frame, while it was not possible to localize experimentally another band origin due to the electronic transition localized on the anisole molecule. The observed structure of the complex is stabilized by a hydrogen bond between the phenol, acting as a proton donor, and the anisole molecule, acting as an acceptor through the lone pairs of the oxygen atom. A secondary interaction involving the hydrogen atoms of the anisole methyl group and the 蟺 electron system of the phenol molecule stabilizes the complex in a nonplanar configuration. Additional insights about the landscapes of the potential energy surfaces governing the ground and first excited electronic states of the anisole鈥損henol complex, with the issuing implications on the system photodynamic, can be extracted from the combined experimental and computational studies.