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Title: Modeling solvation effects in real-space and real-time within density functional approaches

Abstract

The Polarizable Continuum Model (PCM) can be used in conjunction with Density Functional Theory (DFT) and its time-dependent extension (TDDFT) to simulate the electronic and optical properties of molecules and nanoparticles immersed in a dielectric environment, typically liquid solvents. In this contribution, we develop a methodology to account for solvation effects in real-space (and real-time) (TD)DFT calculations. The boundary elements method is used to calculate the solvent reaction potential in terms of the apparent charges that spread over the van der Waals solute surface. In a real-space representation, this potential may exhibit a Coulomb singularity at grid points that are close to the cavity surface. We propose a simple approach to regularize such singularity by using a set of spherical Gaussian functions to distribute the apparent charges. We have implemented the proposed method in the OCTOPUS code and present results for the solvation free energies and solvatochromic shifts for a representative set of organic molecules in water.

Authors:
 [1]; ; ;  [1]
  1. Istituto Nanoscienze - CNR, Centro S3, via Campi 213/A, 41125 Modena (Italy)
Publication Date:
OSTI Identifier:
22489698
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 14; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; DENSITY FUNCTIONAL METHOD; DIELECTRIC MATERIALS; FREE ENERGY; GAUSS FUNCTION; LIQUIDS; MOLECULES; NANOPARTICLES; OPTICAL PROPERTIES; SIMULATION; SINGULARITY; SOLUTES; SOLVATION; SOLVENTS; TIME DEPENDENCE

Citation Formats

Delgado, Alain, Centro de Aplicaciones Tecnológicas y Desarrollo Nuclear, Calle 30 # 502, 11300 La Habana, Corni, Stefano, Pittalis, Stefano, and Rozzi, Carlo Andrea. Modeling solvation effects in real-space and real-time within density functional approaches. United States: N. p., 2015. Web. doi:10.1063/1.4932593.
Delgado, Alain, Centro de Aplicaciones Tecnológicas y Desarrollo Nuclear, Calle 30 # 502, 11300 La Habana, Corni, Stefano, Pittalis, Stefano, & Rozzi, Carlo Andrea. Modeling solvation effects in real-space and real-time within density functional approaches. United States. https://doi.org/10.1063/1.4932593
Delgado, Alain, Centro de Aplicaciones Tecnológicas y Desarrollo Nuclear, Calle 30 # 502, 11300 La Habana, Corni, Stefano, Pittalis, Stefano, and Rozzi, Carlo Andrea. 2015. "Modeling solvation effects in real-space and real-time within density functional approaches". United States. https://doi.org/10.1063/1.4932593.
@article{osti_22489698,
title = {Modeling solvation effects in real-space and real-time within density functional approaches},
author = {Delgado, Alain and Centro de Aplicaciones Tecnológicas y Desarrollo Nuclear, Calle 30 # 502, 11300 La Habana and Corni, Stefano and Pittalis, Stefano and Rozzi, Carlo Andrea},
abstractNote = {The Polarizable Continuum Model (PCM) can be used in conjunction with Density Functional Theory (DFT) and its time-dependent extension (TDDFT) to simulate the electronic and optical properties of molecules and nanoparticles immersed in a dielectric environment, typically liquid solvents. In this contribution, we develop a methodology to account for solvation effects in real-space (and real-time) (TD)DFT calculations. The boundary elements method is used to calculate the solvent reaction potential in terms of the apparent charges that spread over the van der Waals solute surface. In a real-space representation, this potential may exhibit a Coulomb singularity at grid points that are close to the cavity surface. We propose a simple approach to regularize such singularity by using a set of spherical Gaussian functions to distribute the apparent charges. We have implemented the proposed method in the OCTOPUS code and present results for the solvation free energies and solvatochromic shifts for a representative set of organic molecules in water.},
doi = {10.1063/1.4932593},
url = {https://www.osti.gov/biblio/22489698}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 14,
volume = 143,
place = {United States},
year = {Wed Oct 14 00:00:00 EDT 2015},
month = {Wed Oct 14 00:00:00 EDT 2015}
}