Thermodynamic properties of ammonia clusters (NH3)n n = 2-11: comparing classical and quantum simulation results for hydrogen bonded species.
Classical and quantum simulations of ammonia clusters in the dimer through the hendecamer range are performed using the stereographic projection path integral. Employing the most recent polarizable potential to describe intermolecular interactions, energetic and structural data obtained with our simulations provide support for a more fluxional or flexible nature at low temperature of the ammonia dimer, pentamer, and hexamer than in the other investigated species. The octamer and the hendecamer display a relatively strong melting peak in the classical heat capacity and a less intense but significant melting peak in the quantum heat capacity. The latter are shifted to lower temperature (roughly 15 and 40 K lower, respectively) by the quantum effects. The features present in both classical and quantum constant volume heat capacity are interpreted as an indication of melting even in the octamer case, where a large energy gap is present between its global minimum and second most stable species. We develop a first order finite difference algorithm to integrate the geodesic equations in the inertia ellipsoid generated by n rigid nonlinear bodies mapped with stereographic projections. We use the technique to optimize configurations and to explore the potential surface of the hendecamer.
Lubombo
C
C
Department of Chemistry and Physics, Arcadia University, Glenside, Pennsylvania 019038-3295, USA.
Curotto
E
E
Janeiro Barral
Paula E
PE
Mella
Massimo
M
D000641:Ammonia / Q000737:chemistry*; D003198:Computer Simulation; D019281:Dimerization; D006860:Hydrogen Bonding; D008956:Models, Chemical; D011789:Quantum Theory; D013696:Temperature; D013816:Thermodynamics
D000641:Ammonia