A B3LYP and MP2(full) theoretical investigation on the cooperativity effect between cation-molecule and hydrogen-bonding interactions in the O-cresol complex with Na

作者：Yan, Yong-gan; Shi, Wen-jing^*; Feng, Guo-rui; Ren, Fu-de; Wang, Yong

来源：Computational and Theoretical Chemistry, 2012, 996: 91-102.

DOI：10.1016/j.comptc.2012.07.020

• Cooperativity effect
• Cation-molecule interaction
• Hydrogen-bonding interactions
• MP2(full)

The B3LYP/6-311++G(++) and MP2(full)/6-311++G(++) calculations are carried out on the binary complex formed by an O-cresol moiety and a Na+ cation or two O-cresol monomers, as well as the ternary system that contains a Na+ cation and two O-cresol units. The cooperativity effects between the cation-molecule (Na+center dot center dot center dot O and T-shaped Na+center dot center dot center dot pi) and hydrogen-bonding (H center dot center dot center dot O and T-shaped H center dot center dot center dot pi) interactions are investigated. The result shows that the distance R-Na center dot center dot center dot O in ternary system increases when compared to the binary complex while the value of R-Na center dot center dot center dot pi, R-H center dot center dot center dot O or R-H center dot center dot center dot pi in ternary conformation decreases. The cooperativity effect is observed in the conformations formed by the moderate Na+center dot center dot center dot pi, H center dot center dot center dot pi and H center dot center dot center dot O interactions, while the anti-cooperativity effect is present in the complex with the strong Na+center dot center dot center dot O cation-molecule interaction, as one of the coexistent non-covalent interactions in a ternary system. The nature of the cooperativity effect is revealed by the atom in molecule (AIM) and electron density shifts methods.

• 出版日期2012-9-15
• 单位中北大学; 山西医科大学; 太原理工大学