Application of the independent molecule model to the calculation of free energy and rigid-body motions of water hexamers.
The stabilities of five water hexamers (cyclic, boat, book, prism and cage structure) in the gas phase were investigated with the independent molecule model. In this model, the position and orientation of each water molecule within the hexamer are characterized with a translational vector and Eulerian angles, and then each molecule can move freely as a rigid body with respect to the others. Force field energy minimization yielded structures for each hexamer. Normal mode analyses were done on the five hexamers. Hydrogen bond strength in the hexamer decreases in the order: boat, cyclic, book, cage and prism. Hydrogen bond lifetimes also decrease in this order. By estimating the internal energy and the vibrational entropy of rigid-body motions, we determined the temperature dependence of the free energy for each hexamer in the range 100-350 K. Free energy of the hexamers increases in the previously mentioned order also. The most stable hexamer is the boat, and the least stable is the prism. The stabilities of the boat and the cyclic are very similar. The more planar hexamers (cyclic and boat) are more stable than the three-dimensional hexamers (cage and prism). Although the experiments of Liu et al. [Nature 381 (1996) 501] were interpreted in terms of a cage cluster, our calculations indicate boat is more likely.
Yoshioki
Shuzo
S
Yatsushiro National College of Technology, Yatsushiro 866-8501, Japan. yoshioki@as.yatsushiro-nct.ac.jp
D006860:Hydrogen Bonding; D008958:Models, Molecular; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
D014867:Water