First-principles molecular dynamics simulations at solid-liquid interfaces with a continuum solvent
Continuum solvent models have become a standard technique in the context of electronic structure calculations, yet no implementations have been reported capable to perform molecular dynamics at solid-liquid interfaces. We propose here such a continuum approach in a density functional theory framewor...
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paperaa:paper_00219606_v131_n17_p_Sanchez2023-06-12T16:43:20Z First-principles molecular dynamics simulations at solid-liquid interfaces with a continuum solvent J Chem Phys 2009;131(17) Sánchez, V.M. Sued, M. Scherlis, D.A. A-density Acid-base equilibria Atomic coordinate Car-Parrinello molecular dynamics simulations Car-Parrinello simulation Computational costs Constant of motion Continuum model Continuum solvents Dielectric functions Dielectric medium Electronic density Electronic structure calculations Experimental research First-principles Interfacial region Kohn-Sham potential Molecular dynamics simulations Molecular mechanism Multigrid methods Periodic boundary conditions Plane-wave basis set Poisson problem Self-consistent calculation Solid-liquid interfaces TiO Two-dimension Water interface Continuum mechanics Density functional theory Dynamics Electronic structure Liquids Molecular dynamics Poisson equation Simulators Solvents Titanium dioxide Titanium oxides Phase interfaces Continuum solvent models have become a standard technique in the context of electronic structure calculations, yet no implementations have been reported capable to perform molecular dynamics at solid-liquid interfaces. We propose here such a continuum approach in a density functional theory framework using plane-wave basis sets and periodic boundary conditions. Our work stems from a recent model designed for Car-Parrinello simulations of quantum solutes in a dielectric medium [D. A. Scherlis, J. Chem. Phys. 124, 074103 (2006)], for which the permittivity of the solvent is defined as a function of the electronic density of the solute. This strategy turns out to be inadequate for systems extended in two dimensions: the dependence of the dielectric function on the electronic density introduces a new term in the Kohn-Sham potential, which becomes unphysically large at the interfacial region, seriously affecting the convergence of the self-consistent calculations. If the dielectric medium is properly redefined as a function of the atomic coordinates, a good convergence is obtained and the constant of motion is conserved during the molecular dynamics simulations. The Poisson problem is solved using a multigrid method, and in this way Car-Parrinello molecular dynamics simulations of solid-liquid interfaces can be performed at a very moderate computational cost. This scheme is employed to investigate the acid-base equilibrium at the TiO2 -water interface. The aqueous behavior of titania surfaces has stimulated a large amount of experimental research, but many open questions remain concerning the molecular mechanisms determining the chemistry of the interface. Here we make an attempt to answer some of them, putting to the test our continuum model. © 2009 American Institute of Physics. Fil:Sánchez, V.M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Sued, M. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2009 info:eu-repo/semantics/article info:ar-repo/semantics/artículo info:eu-repo/semantics/publishedVersion application/pdf eng info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00219606_v131_n17_p_Sanchez |
institution |
Universidad de Buenos Aires |
institution_str |
I-28 |
repository_str |
R-134 |
collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
language |
Inglés |
orig_language_str_mv |
eng |
topic |
A-density Acid-base equilibria Atomic coordinate Car-Parrinello molecular dynamics simulations Car-Parrinello simulation Computational costs Constant of motion Continuum model Continuum solvents Dielectric functions Dielectric medium Electronic density Electronic structure calculations Experimental research First-principles Interfacial region Kohn-Sham potential Molecular dynamics simulations Molecular mechanism Multigrid methods Periodic boundary conditions Plane-wave basis set Poisson problem Self-consistent calculation Solid-liquid interfaces TiO Two-dimension Water interface Continuum mechanics Density functional theory Dynamics Electronic structure Liquids Molecular dynamics Poisson equation Simulators Solvents Titanium dioxide Titanium oxides Phase interfaces |
spellingShingle |
A-density Acid-base equilibria Atomic coordinate Car-Parrinello molecular dynamics simulations Car-Parrinello simulation Computational costs Constant of motion Continuum model Continuum solvents Dielectric functions Dielectric medium Electronic density Electronic structure calculations Experimental research First-principles Interfacial region Kohn-Sham potential Molecular dynamics simulations Molecular mechanism Multigrid methods Periodic boundary conditions Plane-wave basis set Poisson problem Self-consistent calculation Solid-liquid interfaces TiO Two-dimension Water interface Continuum mechanics Density functional theory Dynamics Electronic structure Liquids Molecular dynamics Poisson equation Simulators Solvents Titanium dioxide Titanium oxides Phase interfaces Sánchez, V.M. Sued, M. Scherlis, D.A. First-principles molecular dynamics simulations at solid-liquid interfaces with a continuum solvent |
topic_facet |
A-density Acid-base equilibria Atomic coordinate Car-Parrinello molecular dynamics simulations Car-Parrinello simulation Computational costs Constant of motion Continuum model Continuum solvents Dielectric functions Dielectric medium Electronic density Electronic structure calculations Experimental research First-principles Interfacial region Kohn-Sham potential Molecular dynamics simulations Molecular mechanism Multigrid methods Periodic boundary conditions Plane-wave basis set Poisson problem Self-consistent calculation Solid-liquid interfaces TiO Two-dimension Water interface Continuum mechanics Density functional theory Dynamics Electronic structure Liquids Molecular dynamics Poisson equation Simulators Solvents Titanium dioxide Titanium oxides Phase interfaces |
description |
Continuum solvent models have become a standard technique in the context of electronic structure calculations, yet no implementations have been reported capable to perform molecular dynamics at solid-liquid interfaces. We propose here such a continuum approach in a density functional theory framework using plane-wave basis sets and periodic boundary conditions. Our work stems from a recent model designed for Car-Parrinello simulations of quantum solutes in a dielectric medium [D. A. Scherlis, J. Chem. Phys. 124, 074103 (2006)], for which the permittivity of the solvent is defined as a function of the electronic density of the solute. This strategy turns out to be inadequate for systems extended in two dimensions: the dependence of the dielectric function on the electronic density introduces a new term in the Kohn-Sham potential, which becomes unphysically large at the interfacial region, seriously affecting the convergence of the self-consistent calculations. If the dielectric medium is properly redefined as a function of the atomic coordinates, a good convergence is obtained and the constant of motion is conserved during the molecular dynamics simulations. The Poisson problem is solved using a multigrid method, and in this way Car-Parrinello molecular dynamics simulations of solid-liquid interfaces can be performed at a very moderate computational cost. This scheme is employed to investigate the acid-base equilibrium at the TiO2 -water interface. The aqueous behavior of titania surfaces has stimulated a large amount of experimental research, but many open questions remain concerning the molecular mechanisms determining the chemistry of the interface. Here we make an attempt to answer some of them, putting to the test our continuum model. © 2009 American Institute of Physics. |
format |
Artículo Artículo publishedVersion |
author |
Sánchez, V.M. Sued, M. Scherlis, D.A. |
author_facet |
Sánchez, V.M. Sued, M. Scherlis, D.A. |
author_sort |
Sánchez, V.M. |
title |
First-principles molecular dynamics simulations at solid-liquid interfaces with a continuum solvent |
title_short |
First-principles molecular dynamics simulations at solid-liquid interfaces with a continuum solvent |
title_full |
First-principles molecular dynamics simulations at solid-liquid interfaces with a continuum solvent |
title_fullStr |
First-principles molecular dynamics simulations at solid-liquid interfaces with a continuum solvent |
title_full_unstemmed |
First-principles molecular dynamics simulations at solid-liquid interfaces with a continuum solvent |
title_sort |
first-principles molecular dynamics simulations at solid-liquid interfaces with a continuum solvent |
publishDate |
2009 |
url |
http://hdl.handle.net/20.500.12110/paper_00219606_v131_n17_p_Sanchez |
work_keys_str_mv |
AT sanchezvm firstprinciplesmoleculardynamicssimulationsatsolidliquidinterfaceswithacontinuumsolvent AT suedm firstprinciplesmoleculardynamicssimulationsatsolidliquidinterfaceswithacontinuumsolvent AT scherlisda firstprinciplesmoleculardynamicssimulationsatsolidliquidinterfaceswithacontinuumsolvent |
_version_ |
1769810162552406016 |