A B3LYP and MP2(full) theoretical investigation on the cooperativity effect between hydrogen-bonding and cation-molecule interactions and thermodynamic property in the 1: 2 (Na+: N-(Hydroxymethyl)acetamide) ternary complex

作者：Feng, Guo-rui; Qi, Ting-ye; Shi, Wen-jing^*; Guo, Yu-xia; Zhang, Yu-jiang; Guo, Jun; Kang, Li-xun

来源：Journal of Molecular Modeling, 2014, 20(3): 2154.

DOI：10.1007/s00894-014-2154-3

• Cation-molecule interaction
• Cooperativity effect
• Hydrogen bond
• MP2
• Thermodynamic cooperativity

The cooperativity effects between the O/N-H center dot center dot center dot O hydrogen-bonding and Na+center dot center dot center dot O cation-molecule interactions in the 1: 2 (Na+: N-(Hydroxymethyl) acetamide) systems were investigated at the B3LYP/6-311++ G**, MP2(full)/6-311++ G** and MP2(full)/aug-cc-pvtz levels. The thermodynamic cooperativity calculations were also carried out for two pathways of the ternary-complex formation. The result shows that, in most ternary complexes, the O/N-H center dot center dot center dot O and Na+center dot center dot center dot O interactions are weakened in comparison with those in binary systems, leading to the anti-cooperativity effects, in particular in the complexes in which only the Na+center dot center dot center dot O interactions exist. Shifts of electron density confirm the existence of anti-cooperativity. The increase of favorable enthalpic contribution leads to the positive cooperativity effect with negative. G(coop) on forming the ternary complex by initial N-(Hydroxymethyl) acetamide dimer followed by addition of Na+. In forming the ternary complex by Na+ N-(Hydroxymethyl) acetamide with the second N-(Hydroxymethyl) acetamide unit, the large unfavorable entropy change leads to the negative cooperativity effect with positive. Delta G(coop). The ternary complex is more easily formed by the pathway in which Na+ binds to N-(Hydroxymethyl) acetamide dimer.

• 出版日期2014-3
• 单位太原理工大学; 山西医科大学