Thermodynamic stability of type-I and type-II clathrate hydrates depending on the chemical species of the guest substances

The free energy differences are calculated for various type-I and type-II clathrate hydrates based on molecular-dynamics simulations, thereby evaluating the thermodynamic stability of the hydrates depending on the chemical species of the guest substances. The simulation systems consist of 27 unit cells, that is, 1242 water molecules and 216 guest molecules for type-I hydrates, and 3672 water molecules and 648 guest molecules for type-II hydrates. The water molecules are described by TIP4P potential, while the guest molecules are described by one-site Lennard-Jones potential, U=4 epsilon{(sigma/r)(12)-(sigma/r)(6)}, where U is the potential energy, r is the particle distance, sigma is the particle diameter, and epsilon is the energy well depth. The optimal values of sigma that yield the minimum free energy (the best thermodynamic stability) were determined to be 0.39 nm for the type-I hydrates and 0.37 nm for the type-II hydrates. (c) 2007 American Institute of Physics.