Spectroscopic and theoretical evidence for the cooperativity between red-shift hydrogen bond and blue-shift hydrogen bond in DMSO aqueous solutions.
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.
Li
Qingzhong
Q
Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005, People's Republic of China. lqz02@mails.tsinghua.edu.cn
An
Xiulin
X
Gong
Baoan
B
Cheng
Jianbo
J
D004121:Dimethyl Sulfoxide / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D012996:Solutions; D013057:Spectrum Analysis; D013816:Thermodynamics; D014732:Vibration; D014867:Water / Q000737:chemistry
D012996:Solutions; D014867:Water; D004121:Dimethyl Sulfoxide