title: Quantum Monte Carlo simulations of selected ammonia clusters (n = 2-5): isotope effects on the ground state of typical hydrogen bonded systems.
abstract: Variational Monte Carlo, diffusion Monte Carlo, and stereographic projection path integral simulations are performed on eight selected species from the (NH(3))(n), (ND(3))(n), (NH(2)D)(n), and (NH(3))(n-1)(ND(3)) clusters. Each monomer is treated as a rigid body with the rotation spaces mapped by the stereographic projection coordinates. We compare the energy obtained from path integral simulations at several low temperatures with those obtained by diffusion Monte Carlo, for two dimers, and we find that at 4 K, the fully deuterated dimer energy is in excellent agreement with the ground state energy of the same. The ground state wavefunction for the (NH(3))(2-5) clusters is predominantly localized in the global minimum of the potential energy. In all simulations of mixed isotopic substitutions, we find that the heavier isotope is almost exclusively the participant in the hydrogen bond.
authors.affiliation: Department of Chemistry and Physics, Arcadia University, Glenside, Pennsylvania 19038-3295, USA. curotto@arcadia.edu
authors.forename: E
authors.initials: E
authors.lastname: Curotto
authors.forename: Massimo
authors.initials: M
authors.lastname: Mella
mesh_terms: D000465:Algorithms; D000641:Ammonia / Q000737:chemistry*; D003903:Deuterium / Q000737:chemistry*; D004058:Diffusion; D019281:Dimerization; D006860:Hydrogen Bonding; D009010:Monte Carlo Method; D011789:Quantum Theory; D012399:Rotation
chemical_list: D000641:Ammonia; D003903:Deuterium