Structures of 1,2,3-trihydroxybenzene in the S₀ and S₁ states

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• 作者：Gier ; H. ; Roth ; W. ; Schumm ; S. ; Gerhards ; M.
• 关键词：Electronically excited states ; CASSCF ; Vibrational coupling ; R2PI spectroscopy ; Hydroxybenzenes
• 刊名：Journal of Molecular Structure
• 出版年：2002
• 出版时间：June 3, 2002
• 年：2002
• 卷：610
• 期：1-3
• 页码：1-16
• 全文大小：452 K

文摘

In this paper we report on the structure and vibrations of gaseous pyrogallol (1,2,3-trihydroxybenzene) in the electronic ground state (S₀) and its first electronically excited state (S₁). Both ab initio CASSCF/CASMP2 calculations as well as R2PI spectroscopy have been performed. From the ab initio calculations three minimum energy structures are obtained and the vibrations of two structures are observed in the R2PI spectra. The minimum energy structures differ by their OH torsional angles. The full three-dimensional potential energy surface of the coupled torsional motions is investigated and the three-dimensional eigenvalues are calculated. The most stable structure of pyrogallol contains two intramolecular hydrogen bonds and turns out to be planar in the S₀ state. In the S₁ state the free OH group is rotated out of the plane of the aromatic ring by about 40°. The strong change in geometry of this structure is predicted by the CASSCF calculations and confirmed by the R2PI spectra of pyrogallol and its deuterated species. The low frequency region of the R2PI spectra can be explained by a torsional motion and the out of plane vibration 17b.