Origin of the Unusual Ultraviolet Absorption of Arsenicin A

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• 作者：Sundaram Arulmozhiraja ; Michelle L. Coote ; Di Lu ; Geoffrey Salem ; S. Bruce Wild
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：May 5, 2011
• 年：2011
• 卷：115
• 期：17
• 页码：4530-4534
• 全文大小：834K
• 年卷期：v.115,no.17(May 5, 2011)
• ISSN：1520-5215

文摘

This paper presents a combined experimental and theoretical study of the electronic spectrum of the natural adamantane-type polyarsenical Arsenicin A. Experiments reveal that this molecule strongly absorbs UV light in the absence of an obvious chromophore. The observed absorbance is supported by the time-dependent density functional (TD-DFT) calculations with B3LYP, M06-L, and M06-2X functionals combined with the 6-311+G(3df,2pd) basis set, as well as by symmetry-adapted cluster/configuration interaction (SAC-CI) theory. The theoretical investigations reveal that the absorption is facilitated by through-space and through-bond interactions, between the lone pairs on the arsenic and oxygen atoms and the 蟽-bonding framework of the molecule, that destabilize occupied and stabilize unoccupied molecular orbitals.