Structure and energetics of ammonia clusters (NH3)n (n = 3-20) investigated using a rigid-polarizable model derived from ab initio calculations.
An analytical model has been developed to describe the interaction between rigid ammonia molecules including the explicit description of induction. The parameters of the model potential were chosen by fitting high quality ab initio data obtained using second-order Møller-Plesset (MP2) perturbation theory and extended basis sets. The description of polarization effects is introduced by using a noniterative form of the "charge on spring model", the latter accounting for more than 95% of the dipole induction energy and of the increased molecular dipole. Putative global minima for (NH3)n (n = 3-20) have been optimized using this new model, the structure and energetics of the clusters with n = 3-5 being found in good agreement with previous ab initio results including electronic correlation. Results for larger species have been compared with previous structural studies where only nonpolarizable models were employed. Our model predicts larger binding energies for any cluster size than previous analytical surfaces, the results often suggesting a reorganization of the relative energy ranking and a different structure for the global minimum.
Janeiro-Barral
Paula E
PE
School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK.
Mella
Massimo
M
Curotto
E
E