화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.101, No.42, 8402-8409, 1997
Molecular-Dynamics Simulation Studies of Zeolite-A .5. Structure and Dynamics of Cations in H-12-A and (CH3NH3)(10)Na-2-A Using Rigid Dehydrated Zeolite-A Frameworks
In the present paper a molecular dynamics simulation technique is applied to study the local structure and dynamics of H+, CH3NH3+, and Na+ ions in rigid dehydrated zeolite-A frameworks using a simple Lennard-Jones potential plus Coulomb potential with Ewald summation. In the H-12-A zeolite system, two structures appear, depending upon the choice of the Lennard-Jones parameter, sigma, for the H+ ion. For the smaller values of sigma, the 12th H+ ion is located on one of the 8-ring window sites which are already occupied by three H+ ions; for the larger values of sigma, it is at one of the opposite-4-ring sites with the remaining 11 H+ ions almost fixed near their initial positions. In the (CH3NH3)(10)Na-2-A zeolite system, the main structural differences from an X-ray crystallographic report are 4-fold : no facing CH3NH3+ ions through a 6-ring window, two ions in the beta-cage, the appearance of a CH3NH3+ ion on one of the opposite-4-ring sites, and the lying of CH3NH3+ ions on the planes of the 8-ring window sites. Four kinds of time correlation functions for the CH3NH3+ ions show the dynamics of the ions, reflecting the different structural arrangements of the ions well. The analyses of hydrogen bond time correlation functions for the four nonequivalent CH3NH3+ ions indicate that about 0.8, 2.9, 0.6, 2.9, 1.6, 0.9, 1.7, and 2.0 hydrogen bonds formed between I and O(2), I and O(3), II and O(2), II and O(3), III and O(I), III and O(2), IV and O(I), and IV and O(3) are retained for 0.83, 1.89, 0.63, 1.61, 0.42, 0.31, 1.11, and 1.26 ps, respectively, before a breaking of the hydrogen bond occurs, leading to a significant exchange of O atoms hydrogen-bonded to the ion.