Dynamical aspects of intermolecular proton transfer in liquid water and low-density amorphous ices

The microscopic dynamics of an excess proton in water and in low-density amorphous ices has been studied by means of a series of molecular dynamics simulations. Interaction of water with the proton species was modelled using a multistate empirical valence bond Hamiltonian model. The analysis of the...

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Detalhes bibliográficos
Autores: Tahat, Amani, Martí Rabassa, Jordi|||0000-0002-3721-9634
Tipo de documento: artigo
Data de publicação:2014
País:España
Recursos:Universitat Politècnica de Catalunya (UPC)
Repositório:UPCommons. Portal del coneixement obert de la UPC
Idioma:inglês
OAI Identifier:oai:upcommons.upc.edu:2117/23020
Acesso em linha:https://hdl.handle.net/2117/23020
https://dx.doi.org/10.1103/PhysRevE.89.052130
Access Level:Acceso aberto
Palavra-chave:Molecular dynamics
Proton transfer reactions
microscopic dynamics
excess proton in water
low-density amorphous ices
proton transfer
Dinàmica molecular
Protons -- Reaccions de transferència
Àrees temàtiques de la UPC::Física
Descrição
Resumo:The microscopic dynamics of an excess proton in water and in low-density amorphous ices has been studied by means of a series of molecular dynamics simulations. Interaction of water with the proton species was modelled using a multistate empirical valence bond Hamiltonian model. The analysis of the effects of low temperatures on proton diffusion and transfer rates has been considered for a temperature range between 100 and 298 K at the constant density of 1 g cm -3 . We observed a marked slowdown of proton transfer rates at low temperatures, but some episodes are still seen at 100 K. In a similar fashion, mobility of the lone proton gets significantly reduced when temperature decreases below 273 K. The proton transfer in low-density amorphous ice is an activated process with energy barriers between 1–10 kJ/mol depending of the temperature range considered and eventually showing Arrhenius-like behavior. Spectroscopic data indicated the survival of both Zundel and Eigen structures along the whole temperature range, revealed by significant spectral frequency shifts.