Hybrid Quantum Classical Molecular Dynamics Simulation of the Proton-Transfer Reaction of HO- with HBr in Aqueous Clusters

A hybrid quantum classical computational algorithm, which couples a density functional Hamiltonian to a classical bath, is applied to investigate the proton-transfer reaction OH- + HBr → H2O + Br- in aqueous clusters. The reagent was modeled using density functional theory with a Gaussian basis set;...

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Autores principales: Elola, María Dolores, Estrin, Dario Ariel, Laria, Daniel Hector
Publicado: 1999
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v103_n26_p5105_Elola
http://hdl.handle.net/20.500.12110/paper_10895639_v103_n26_p5105_Elola
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling paper:paper_10895639_v103_n26_p5105_Elola2023-06-08T16:06:15Z Hybrid Quantum Classical Molecular Dynamics Simulation of the Proton-Transfer Reaction of HO- with HBr in Aqueous Clusters Elola, María Dolores Estrin, Dario Ariel Laria, Daniel Hector A hybrid quantum classical computational algorithm, which couples a density functional Hamiltonian to a classical bath, is applied to investigate the proton-transfer reaction OH- + HBr → H2O + Br- in aqueous clusters. The reagent was modeled using density functional theory with a Gaussian basis set; two different force fields for the classical bath were investigated: the TIP4P-FQ fluctuating charge and the TIP4P mean field potentials. Basis sets, functionals, and force field parameters have been validated by performing calculations on [HO-](H2O), [Br-](H2O), [HBr](H2O), and [H2O](H2O) isolated dimers at 0 K. Molecular dynamics simulations of the system [HOHBr]-(H2O)n, with n = 2 and 6, show that the reaction is spontaneous and rather exothermic, leading to the full detachment of the bromide ion from the halide and the generation of a water molecule within a few femtoseconds. In addition, our experiments show that the process involves a fast damping of the potential energy concomitant with a sudden increase of the vibrational kinetic energy of the newly formed HO bond in the water molecule. The gradual dissipation of the solute energy into the classical region led to an increase in the cluster sizes, suggesting the onset of cluster fragmentation; both phenomena evolve faster in the smallest clusters. The role of polarization effects in the classical subsystem on the reaction dynamics was also investigated by performing simulation experiments with the TIP4P potential. In these cases, the proton transfer is more exothermic, leading to fragmentation of the aggregates at earlier stages. Fil:Elola, M.D. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Estrin, D.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Laria, D. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 1999 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v103_n26_p5105_Elola http://hdl.handle.net/20.500.12110/paper_10895639_v103_n26_p5105_Elola
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description A hybrid quantum classical computational algorithm, which couples a density functional Hamiltonian to a classical bath, is applied to investigate the proton-transfer reaction OH- + HBr → H2O + Br- in aqueous clusters. The reagent was modeled using density functional theory with a Gaussian basis set; two different force fields for the classical bath were investigated: the TIP4P-FQ fluctuating charge and the TIP4P mean field potentials. Basis sets, functionals, and force field parameters have been validated by performing calculations on [HO-](H2O), [Br-](H2O), [HBr](H2O), and [H2O](H2O) isolated dimers at 0 K. Molecular dynamics simulations of the system [HOHBr]-(H2O)n, with n = 2 and 6, show that the reaction is spontaneous and rather exothermic, leading to the full detachment of the bromide ion from the halide and the generation of a water molecule within a few femtoseconds. In addition, our experiments show that the process involves a fast damping of the potential energy concomitant with a sudden increase of the vibrational kinetic energy of the newly formed HO bond in the water molecule. The gradual dissipation of the solute energy into the classical region led to an increase in the cluster sizes, suggesting the onset of cluster fragmentation; both phenomena evolve faster in the smallest clusters. The role of polarization effects in the classical subsystem on the reaction dynamics was also investigated by performing simulation experiments with the TIP4P potential. In these cases, the proton transfer is more exothermic, leading to fragmentation of the aggregates at earlier stages.
author Elola, María Dolores
Estrin, Dario Ariel
Laria, Daniel Hector
spellingShingle Elola, María Dolores
Estrin, Dario Ariel
Laria, Daniel Hector
Hybrid Quantum Classical Molecular Dynamics Simulation of the Proton-Transfer Reaction of HO- with HBr in Aqueous Clusters
author_facet Elola, María Dolores
Estrin, Dario Ariel
Laria, Daniel Hector
author_sort Elola, María Dolores
title Hybrid Quantum Classical Molecular Dynamics Simulation of the Proton-Transfer Reaction of HO- with HBr in Aqueous Clusters
title_short Hybrid Quantum Classical Molecular Dynamics Simulation of the Proton-Transfer Reaction of HO- with HBr in Aqueous Clusters
title_full Hybrid Quantum Classical Molecular Dynamics Simulation of the Proton-Transfer Reaction of HO- with HBr in Aqueous Clusters
title_fullStr Hybrid Quantum Classical Molecular Dynamics Simulation of the Proton-Transfer Reaction of HO- with HBr in Aqueous Clusters
title_full_unstemmed Hybrid Quantum Classical Molecular Dynamics Simulation of the Proton-Transfer Reaction of HO- with HBr in Aqueous Clusters
title_sort hybrid quantum classical molecular dynamics simulation of the proton-transfer reaction of ho- with hbr in aqueous clusters
publishDate 1999
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v103_n26_p5105_Elola
http://hdl.handle.net/20.500.12110/paper_10895639_v103_n26_p5105_Elola
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AT estrindarioariel hybridquantumclassicalmoleculardynamicssimulationoftheprotontransferreactionofhowithhbrinaqueousclusters
AT lariadanielhector hybridquantumclassicalmoleculardynamicssimulationoftheprotontransferreactionofhowithhbrinaqueousclusters
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