Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz
Abstract
Continuum solvation models enable electronic structure calculations of systems in liquid environments, but because of the large number of empirical parameters, they are limited to the class of systems in their fit set (typically organic molecules). Here, we derive a solvation model with no empirical parameters for the dielectric response by taking the linear response limit of a classical density functional for molecular liquids. This model directly incorporates the nonlocal dielectric response of the liquid using an angular momentum expansion, and with a single fit parameter for dispersion contributions it predicts solvation energies of neutral molecules with a RMS error of 1.3 kcal/mol in water and 0.8 kcal/mol in chloroform and carbon tetrachloride. We show that this model is more accurate for strongly polar and charged systems than previous solvation models because of the parameter-free electric response, and demonstrate its suitability for ab initio solvation, including self-consistent solvation in quantum Monte Carlo calculations.
- Authors:
-
- Cornell Univ., Ithaca, NY (United States). Dept. of Physics
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Energy Materials Center at Cornell (EMC2)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1370450
- Alternate Identifier(s):
- OSTI ID: 1228514
- Grant/Contract Number:
- SC0001086
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 142; Journal Issue: 5; Related Information: Emc2 partners with Cornell University (lead); Lawrence Berkeley National Laboratory; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
Citation Formats
Sundararaman, Ravishankar, Schwarz, Kathleen A., Letchworth-Weaver, Kendra, and Arias, T. A. Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz. United States: N. p., 2015.
Web. doi:10.1063/1.4906828.
Sundararaman, Ravishankar, Schwarz, Kathleen A., Letchworth-Weaver, Kendra, & Arias, T. A. Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz. United States. https://doi.org/10.1063/1.4906828
Sundararaman, Ravishankar, Schwarz, Kathleen A., Letchworth-Weaver, Kendra, and Arias, T. A. Tue .
"Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz". United States. https://doi.org/10.1063/1.4906828. https://www.osti.gov/servlets/purl/1370450.
@article{osti_1370450,
title = {Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz},
author = {Sundararaman, Ravishankar and Schwarz, Kathleen A. and Letchworth-Weaver, Kendra and Arias, T. A.},
abstractNote = {Continuum solvation models enable electronic structure calculations of systems in liquid environments, but because of the large number of empirical parameters, they are limited to the class of systems in their fit set (typically organic molecules). Here, we derive a solvation model with no empirical parameters for the dielectric response by taking the linear response limit of a classical density functional for molecular liquids. This model directly incorporates the nonlocal dielectric response of the liquid using an angular momentum expansion, and with a single fit parameter for dispersion contributions it predicts solvation energies of neutral molecules with a RMS error of 1.3 kcal/mol in water and 0.8 kcal/mol in chloroform and carbon tetrachloride. We show that this model is more accurate for strongly polar and charged systems than previous solvation models because of the parameter-free electric response, and demonstrate its suitability for ab initio solvation, including self-consistent solvation in quantum Monte Carlo calculations.},
doi = {10.1063/1.4906828},
journal = {Journal of Chemical Physics},
number = 5,
volume = 142,
place = {United States},
year = {Tue Feb 03 00:00:00 EST 2015},
month = {Tue Feb 03 00:00:00 EST 2015}
}
Web of Science
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Workhorse Semilocal Density Functional for Condensed Matter Physics and Quantum Chemistry
journal, July 2009
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 103, Issue 2
Smooth relativistic Hartree–Fock pseudopotentials for H to Ba and Lu to Hg
journal, May 2005
- Trail, J. R.; Needs, R. J.
- The Journal of Chemical Physics, Vol. 122, Issue 17
General parameterized SCF model for free energies of solvation in aqueous solution
journal, October 1991
- Cramer, Christopher J.; Truhlar, Donald G.
- Journal of the American Chemical Society, Vol. 113, Issue 22
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009
- Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
- The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
Consistent van der Waals Radii for the Whole Main Group
journal, May 2009
- Mantina, Manjeera; Chamberlin, Adam C.; Valero, Rosendo
- The Journal of Physical Chemistry A, Vol. 113, Issue 19
Self-consistent continuum solvation (SCCS): The case of charged systems
journal, December 2013
- Dupont, C.; Andreussi, O.; Marzari, N.
- The Journal of Chemical Physics, Vol. 139, Issue 21
A recipe for free-energy functionals of polarizable molecular fluids
journal, April 2014
- Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Arias, T. A.
- The Journal of Chemical Physics, Vol. 140, Issue 14
New Model for Calculation of Solvation Free Energies: Correction of Self-Consistent Reaction Field Continuum Dielectric Theory for Short-Range Hydrogen-Bonding Effects
journal, January 1996
- Marten, Bryan; Kim, Kyungsun; Cortis, Christian
- The Journal of Physical Chemistry, Vol. 100, Issue 28
The importance of nonlinear fluid response in joint density-functional theory studies of battery systems
journal, October 2013
- Gunceler, Deniz; Letchworth-Weaver, Kendra; Sundararaman, Ravishankar
- Modelling and Simulation in Materials Science and Engineering, Vol. 21, Issue 7
Inhomogeneous Electron Gas
journal, November 1964
- Hohenberg, P.; Kohn, W.
- Physical Review, Vol. 136, Issue 3B, p. B864-B871
Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models
journal, October 2014
- Sundararaman, Ravishankar; Gunceler, Deniz; Arias, T. A.
- The Journal of Chemical Physics, Vol. 141, Issue 13
Field-Extremum Model for Short-Range Contributions to Hydration Free Energy
journal, October 2011
- Pomogaeva, Anna; Chipman, Daniel M.
- Journal of Chemical Theory and Computation, Vol. 7, Issue 12
Towards an assessment of the accuracy of density functional theory for first principles simulations of water
journal, January 2004
- Grossman, Jeffrey C.; Schwegler, Eric; Draeger, Erik W.
- The Journal of Chemical Physics, Vol. 120, Issue 1
Van der Waals Density Functional for General Geometries
journal, June 2004
- Dion, M.; Rydberg, H.; Schröder, E.
- Physical Review Letters, Vol. 92, Issue 24
Norm-conserving Hartree–Fock pseudopotentials and their asymptotic behavior
journal, January 2005
- Trail, J. R.; Needs, R. J.
- The Journal of Chemical Physics, Vol. 122, Issue 1
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
Evaluation of Solvent Effects in Isotropic and Anisotropic Dielectrics and in Ionic Solutions with a Unified Integral Equation Method: Theoretical Bases, Computational Implementation, and Numerical Applications
journal, December 1997
- Mennucci, B.; Cancès, E.; Tomasi, J.
- The Journal of Physical Chemistry B, Vol. 101, Issue 49
Accurate First Principles Calculation of Molecular Charge Distributions and Solvation Energies from Ab Initio Quantum Mechanics and Continuum Dielectric Theory
journal, December 1994
- Tannor, David J.; Marten, Bryan; Murphy, Robert
- Journal of the American Chemical Society, Vol. 116, Issue 26
Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton
journal, August 2006
- Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.
- The Journal of Physical Chemistry B, Vol. 110, Issue 32
Revised self-consistent continuum solvation in electronic-structure calculations
journal, February 2012
- Andreussi, Oliviero; Dabo, Ismaila; Marzari, Nicola
- The Journal of Chemical Physics, Vol. 136, Issue 6
Self-interaction correction to density-functional approximations for many-electron systems
journal, May 1981
- Perdew, J. P.; Zunger, Alex
- Physical Review B, Vol. 23, Issue 10, p. 5048-5079
Continuous surface charge polarizable continuum models of solvation. I. General formalism
journal, March 2010
- Scalmani, Giovanni; Frisch, Michael J.
- The Journal of Chemical Physics, Vol. 132, Issue 11
The implementation of density functional theory within the polarizable continuum model for solvation
journal, December 1994
- Fortunelli, Alessandro; Tomasi, Jacopo
- Chemical Physics Letters, Vol. 231, Issue 1
The radial distribution functions of water and ice from 220 to 673 K and at pressures up to 400 MPa
journal, August 2000
- Soper, A. K.
- Chemical Physics, Vol. 258, Issue 2-3
Quantum Mechanical Continuum Solvation Models
journal, August 2005
- Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
- Chemical Reviews, Vol. 105, Issue 8
Joint density-functional theory for electronic structure of solvated systems
journal, May 2007
- Petrosyan, S. A.; Briere, Jean-Francois; Roundy, David
- Physical Review B, Vol. 75, Issue 20
Framework for solvation in quantum Monte Carlo
journal, May 2012
- Schwarz, Kathleen A.; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra
- Physical Review B, Vol. 85, Issue 20
Self-Consistent Reaction Field Model for Aqueous and Nonaqueous Solutions Based on Accurate Polarized Partial Charges
journal, October 2007
- Marenich, Aleksandr V.; Olson, Ryan M.; Kelly, Casey P.
- Journal of Chemical Theory and Computation, Vol. 3, Issue 6
Joint density functional theory of the electrode-electrolyte interface: Application to fixed electrode potentials, interfacial capacitances, and potentials of zero charge
journal, August 2012
- Letchworth-Weaver, Kendra; Arias, T. A.
- Physical Review B, Vol. 86, Issue 7
Self-Consistent-Field Calculation of Pauli Repulsion and Dispersion Contributions to the Solvation Free Energy in the Polarizable Continuum Model
journal, February 1997
- Amovilli, Claudio; Mennucci, Benedetta
- The Journal of Physical Chemistry B, Vol. 101, Issue 6
Continuum variational and diffusion quantum Monte Carlo calculations
journal, December 2009
- Needs, R. J.; Towler, M. D.; Drummond, N. D.
- Journal of Physics: Condensed Matter, Vol. 22, Issue 2
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138
A new definition of cavities for the computation of solvation free energies by the polarizable continuum model
journal, August 1997
- Barone, Vincenzo; Cossi, Maurizio; Tomasi, Jacopo
- The Journal of Chemical Physics, Vol. 107, Issue 8
Inhomogeneous Electron Gas
journal, March 1973
- Rajagopal, A. K.; Callaway, J.
- Physical Review B, Vol. 7, Issue 5
Quantum Mechanical Continuum Solvation Models
journal, October 2005
- Tomasi, Jacopo; Menucci, Benedetta; Cammi, Roberto
- ChemInform, Vol. 36, Issue 42
Workhorse Semilocal Density Functional for Condensed Matter Physics and Quantum Chemistry
preprint, January 2009
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gabor I.
- arXiv
Framework for solvation in quantum Monte Carlo
text, January 2012
- Schwarz, Kathleen A.; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra
- arXiv
The importance of nonlinear fluid response in joint density-functional theory studies of battery systems
text, January 2013
- Gunceler, Deniz; Letchworth-Weaver, Kendra; Sundararaman, Ravishankar
- arXiv
A recipe for free-energy functionals of polarizable molecular fluids
text, January 2014
- Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Arias, T. A.
- arXiv
Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models
text, January 2014
- Sundararaman, Ravishankar; Gunceler, Deniz; Arias, T. A.
- arXiv
Works referencing / citing this record:
Simulation of Many-Electron Systems That Exchange Matter with the Environment: Simulation of Many-Electron Systems That Exchange Matter with the Environment
journal, August 2018
- Delle Site, Luigi
- Advanced Theory and Simulations, Vol. 1, Issue 10
Computational Insights into Materials and Interfaces for Capacitive Energy Storage
journal, April 2017
- Zhan, Cheng; Lian, Cheng; Zhang, Yu
- Advanced Science, Vol. 4, Issue 7
Development of reaction–diffusion DFT and its application to catalytic oxidation of NO in porous materials
journal, November 2019
- Liu, Yu; Liu, Honglai
- AIChE Journal, Vol. 66, Issue 2
Computational Approaches to Photoelectrode Design through Molecular Functionalization for Enhanced Photoelectrochemical Water Splitting
journal, November 2018
- Iyer, Ashwathi; Kearney, Kara; Ertekin, Elif
- ChemSusChem, Vol. 12, Issue 9
Continuum embeddings in condensed-matter simulations
journal, October 2018
- Andreussi, Oliviero; Fisicaro, Giuseppe
- International Journal of Quantum Chemistry, Vol. 119, Issue 1
Modelling heterogeneous interfaces for solar water splitting
journal, January 2017
- Pham, Tuan Anh; Ping, Yuan; Galli, Giulia
- Nature Materials, Vol. 16, Issue 4
Computational optimization of electric fields for better catalysis design
journal, September 2018
- Welborn, Valerie Vaissier; Ruiz Pestana, Luis; Head-Gordon, Teresa
- Nature Catalysis, Vol. 1, Issue 9
Formic acid oxidation on platinum: a simple mechanistic study
journal, January 2015
- Schwarz, Kathleen A.; Sundararaman, Ravishankar; Moffat, Thomas P.
- Physical Chemistry Chemical Physics, Vol. 17, Issue 32
The charge-asymmetric nonlocally determined local-electric (CANDLE) solvation model
journal, February 2015
- Sundararaman, Ravishankar; Goddard, William A.
- The Journal of Chemical Physics, Vol. 142, Issue 6
First-principles electrostatic potentials for reliable alignment at interfaces and defects
journal, March 2017
- Sundararaman, Ravishankar; Ping, Yuan
- The Journal of Chemical Physics, Vol. 146, Issue 10
Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry
journal, March 2017
- Sundararaman, Ravishankar; Goddard, William A.; Arias, Tomas A.
- The Journal of Chemical Physics, Vol. 146, Issue 11
Substrate effects on charged defects in two-dimensional materials
journal, August 2019
- Wang, Dan; Sundararaman, Ravishankar
- Physical Review Materials, Vol. 3, Issue 8
First-principles identification of localized trap states in polymer nanocomposite interfaces
journal, February 2020
- Shandilya, Abhishek; Schadler, Linda S.; Sundararaman, Ravishankar
- Journal of Materials Research, Vol. 35, Issue 8
First-principles electrostatic potentials for reliable alignment at interfaces and defects
text, January 2016
- Sundararaman, Ravishankar; Ping, Yuan
- arXiv
Grand canonical electronic density-functional theory: algorithms and applications to electrochemistry
text, January 2017
- Sundararaman, Ravishankar; Goddard, William A.; Arias, Tomas A.
- arXiv
Computational Insights into Materials and Interfaces for Capacitive Energy Storage
journal, April 2017
- Zhan, Cheng; Lian, Cheng; Zhang, Yu
- Advanced Science, Vol. 4, Issue 7
Solvent-Aware Interfaces in Continuum Solvation
journal, January 2019
- Andreussi, Oliviero; Hörmann, Nicolas Georg; Nattino, Francesco
- Journal of Chemical Theory and Computation, Vol. 15, Issue 3
The charge-asymmetric nonlocally-determined local-electric (CANDLE) solvation model
text, January 2014
- Sundararaman, Ravishankar; Goddard, William A.
- arXiv