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Spectroscopic and theoretical evidence for the cooperativity between red-shift hydrogen bond and blue-shift hydrogen
Qingzhong Li1, Xiulin An, Baoan Gong
1Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005, People's Republic of China. lqz02@mails.tsinghua.edu.cn
Abstract:
The cooperativity between red-shifted hydrogen bond and blue-shifting hydrogen bond in dimethyl sulfoxide aqueous solutions was studied by methods of quantum chemical calculations and infrared spectroscopy. The water molecule plays a different role in two types of hydrogen bonds: proton-donor in red-shifted hydrogen bond and proton-acceptor in blue-shifting hydrogen bond. The cooperativity is not prominent if the ring structure is formed through the OHcdots, three dots, centeredOS H-bond and CHcdots, three dots, centeredO(w) H-bond. However, if the methyl groups in the above ring structure participate in second CHcdots, three dots, centeredO(w) H-bond, the cooperativity is increased. The second CHcdots, three dots, centeredO(w) H-bond enhances OHcdots, three dots, centeredOS H-bond and weakens the first CHcdots, three dots, centeredO(w) H-bond.
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