Deciphering the role of multiple hydrogen bonding sites on the microsolvation of 3-(phenylamino)-2-cyclohexen-1-one with water in the excited states

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• 作者：Ramprasad Misra ; D.K. Maity ; S.P. Bhattacharyya
• 关键词：Excited state ; Microcluster ; Charge transfer ; Hydrogen bonding
• 刊名：Chemical Physics
• 出版年：8 November, 2013
• 年：2013
• 卷：425
• 期：Complete
• 页码：148-155
• 全文大小：1090 K

文摘

We report here our investigations on the H-bonding modifications of molecular electronic structures and properties of 3-(phenylamino)-2-cyclohexen-1-one (PACO) and its 1:3 microhydrated cluster in the ground (S₀) and first two excited states (S₁ and S₂). The changes in bond lengths, atomic charges, natural bond order and aromaticity in the S₀, S₁ and S₂ states have been analysed. The electronic state dependence of the hydrogen bonding strengths at different H-bonding sites of PACO has been looked into. The hydrogen bonds formed through the H-bond accepting carbonyl moiety in PACO.3H₂O cluster appears to get weaker in the excited states while that formed through the H-bond donating amino moiety gets much stronger, compared to their ground state counterpart. The simultaneous strengthening of H-bonds at one site and weakening at another in the S₁ and S₂ states may have link to the overall stabilization of the clusters in the excited states relative to the ground state as observed experimentally.