Communication: Isotopic effects on tunneling motions in the water trimer

We present results of ring polymer molecular dynamics simulations that shed light on the effects of nuclear quantum fluctuations on tunneling motions in cyclic [H2O]3 and [D2O]3, at the representative temperature of T = 75 K. In particular, we focus attention on free energies associated with two key...

Descripción completa

Guardado en:
Detalles Bibliográficos
Autores principales: Videla, P.E., Rossky, P.J., Laria, D.
Formato: JOUR
Materias:
Dangling bonds
Free energy
Hydrogen bonds
Molecules
Quantum electronics
Characteristic time
Isotopic effects
Molecular dynamics simulations
Quantum fluctuation
Transition state approximations
Tunneling effects
Tunneling motion
Zero-point energies
Molecular dynamics
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_00219606_v144_n6_p_Videla
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
Descripción
Sumario:We present results of ring polymer molecular dynamics simulations that shed light on the effects of nuclear quantum fluctuations on tunneling motions in cyclic [H2O]3 and [D2O]3, at the representative temperature of T = 75 K. In particular, we focus attention on free energies associated with two key isomerization processes: The first one corresponds to flipping transitions of dangling OH bonds, between up and down positions with respect to the O-O-O plane of the cluster; the second involves the interchange between connecting and dangling hydrogen bond character of the H-atoms in a tagged water molecule. Zero point energy and tunneling effects lead to sensible reductions of the free energy barriers. Due to the lighter nature of the H nuclei, these modifications are more marked in [H2O]3 than in [D2O]3. Estimates of the characteristic time scales describing the flipping transitions are consistent with those predicted based on standard transition-state-approximation arguments. © 2016 AIP Publishing LLC.

Ejemplares similares