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Title: Charged-cell periodic DFT simulations via an impurity model based on density embedding: Application to the ionization potential of liquid water

Journal Article · · International Journal of Quantum Chemistry
DOI:https://doi.org/10.1002/qua.25801· OSTI ID:1612947
 [1]; ORCiD logo [2];  [3]; ORCiD logo [3]
  1. Rutgers Univ., Newark, NJ (United States); Westfälische Wilhelms Univ., Münster (Germany). Theoretische Organische Chemie, Organisch-Chemisches Inst., Center for Multiscale Theory and Computation (CMTC),
  2. Univ. de Lille (France). CNRS, UMR, Physique des Lasers, Atomes et Molécules (PhLAM)
  3. Rutgers Univ., Newark, NJ (United States)
+ Show Author Affiliations

Abstract Calculations of charged systems in periodic boundary conditions (PBC) are problematic because there are spurious interactions between the charges in different periodic images that can affect the physical picture. In addition, the intuitive limit of Coulomb interactions decaying to zero as the interacting charges are placed at infinite separation no longer applies, and for example total energies become undefined. Leveraging subsystem density functional theory (also known as density embedding) we define an impurity model that embeds a finite neutral or charged subsystem within an extended (infinite) surrounding subsystem. The combination of the impurity model and a consistent choice of the Coulomb reference provides us with an algorithm for evaluating the ionization potential (IP) in extended systems. We demonstrate our approach in a pilot calculation of the IP of liquid water, based on a configuration from a prior ab initio molecular dynamics (AIMD) simulation of liquid water (Genova et al., J. Chem. Phys. 2016, 144, 234105). The calculations with the impurity model capture the broadening on the ionization energies introduced by the interactions between the water molecules. Furthermore, the calculated average IP value (10.5 eV) compare favorably to experiments (9.9‐10.06 eV) and very recent simulations based on the GW approximation (10.55 eV), while at the same time outperforming density embedding calculations carried out with a naïve handling of the electrostatic interactions (about 7 eV).

Research Organization:
Rutgers Univ., Piscataway, NJ (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); French National Research Agency (ANR)
Grant/Contract Number:
SC0018343; ANR-11-LABX-0005-01; DE‐SC0018343
OSTI ID:
1612947
Alternate ID(s):
OSTI ID: 1479563
Journal Information:
International Journal of Quantum Chemistry, Vol. 119, Issue 1; ISSN 0020-7608
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science

References (75)

Spectral functions of the uniform electron gas via coupled-cluster theory and comparison to the G W and related approximations journal June 2016
Generalized Gradient Approximation Made Simple journal October 1996
Error estimates for density-functional theory predictions of surface energy and work function journal December 2016
Photoelectron Spectra of Aqueous Solutions from First Principles journal May 2016
An Efficient Real Space Multigrid QM/MM Electrostatic Coupling journal November 2005
Photoelectron emission spectroscopy of liquid water journal October 1981
Accurate ab initio energetics of extended systems via explicit correlation embedded in a density functional environment journal October 1998
Spin densities from subsystem density-functional theory: Assessment and application to a photosynthetic reaction center complex model journal May 2012
Subsystem-DFT potential-energy curves for weakly interacting systems journal January 2015
Electron affinity of liquid water journal January 2018
Theoretical study of band offsets at semiconductor interfaces journal May 1987
Fully Ab Initio Finite-Size Corrections for Charged-Defect Supercell Calculations journal January 2009
Self-consistent continuum solvation (SCCS): The case of charged systems journal December 2013
Origin of the Energy Barrier to Chemical Reactions of O 2 on Al(111): Evidence for Charge Transfer, Not Spin Selection journal November 2012
Combining the lattice-sum and reaction-field approaches for evaluating long-range electrostatic interactions in molecular simulations journal July 2005
Periodic boundary conditions in ab initio calculations journal February 1995
Electrostatic interactions in finite systems treated with periodic boundary conditions: Application to linear-scaling density functional theory journal November 2011
Gradient-free and gradient-dependent approximations in the total energy bifunctional for weakly overlapping electron densities journal February 2003
Chemistry with ADF journal January 2001
Comparative Study of Benzene···X (X = O 2 , N 2 , CO) Complexes Using Density Functional Theory:  The Importance of an Accurate Exchange−Correlation Energy Density at High Reduced Density Gradients journal October 1997
eQE: An open-source density functional embedding theory code for the condensed phase: GENOVA et al. journal May 2017
Generalized Gradient Approximations of the Noninteracting Kinetic Energy from the Semiclassical Atom Theory: Rationalization of the Accuracy of the Frozen Density Embedding Theory for Nonbonded Interactions journal July 2011
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient journal January 1993
Self-Consistent-Field Wave Functions for Hole States of Some Ne-Like and Ar-Like Ions journal August 1965
Subsystem density-functional theory: Subsystem density-functional theory journal July 2014
Modeling environment effects on spectroscopies through QM/classical models journal January 2013
Subsystem density-functional theory as an effective tool for modeling ground and excited states, their dynamics and many-body interactions journal April 2015
Alignment of Redox Levels at Semiconductor–Water Interfaces journal December 2017
Electronic Levels of Excess Electrons in Liquid Water journal April 2017
Pseudopotentials periodic table: From H to Pu journal December 2014
Theory of Polarization: A Modern Approach book January 2007
GW and Bethe-Salpeter study of small water clusters journal January 2016
Avoiding fractional electrons in subsystem DFT based ab-initio molecular dynamics yields accurate models for liquid water and solvated OH radical journal June 2016
A reciprocal space based method for treating long range interactions in ab initio and force-field-based calculations in clusters journal February 1999
Quantum Mechanical Continuum Solvation Models journal August 2005
Band alignment of semiconductors from density-functional theory and many-body perturbation theory journal October 2014
Electrostatics of solvated systems in periodic boundary conditions journal December 2014
Polarization around an ion in a dielectric continuum with truncated electrostatic interactions journal June 1999
First-principles calculations for defects and impurities: Applications to III-nitrides journal April 2004
Particle mesh Ewald: An N ⋅log( N ) method for Ewald sums in large systems journal June 1993
Orientation dependence of the work function for metal nanocrystals journal December 2017
Valence Electronic Structure of Aqueous Solutions: Insights from Photoelectron Spectroscopy journal May 2016
Calculated electron affinities of the elements journal March 1982
Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena journal February 1995
Resolving the Optical Spectrum of Water: Coordination and Electrostatic Effects journal May 2008
Band offset formation at semiconductor heterojunctions through density-based minimization of interface energy journal August 2016
Modelling charge transfer reactions with the frozen density embedding formalism journal December 2011
On the calculation of multiplet energies by the hartree-fock-slater method journal January 1977
Full Valence Band Photoemission from Liquid Water Using EUV Synchrotron Radiation journal April 2004
Semilocal and hybrid density embedding calculations of ground-state charge-transfer complexes journal March 2013
Electrostatics in periodic boundary conditions and real-space corrections journal March 2008
Exact kinetic energy enables accurate evaluation of weak interactions by the FDE-vdW method journal August 2015
Perspective: Kohn-Sham density functional theory descending a staircase journal October 2016
Assessment of the Perdew–Burke–Ernzerhof exchange-correlation functional journal March 1999
Optical Absorption of Water: Coulomb Effects versus Hydrogen Bonding journal January 2005
Response to “Comment on ‘Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds’” [J. Chem. Phys. 135, 027101 (2011)] journal July 2011
Communication: Avoiding unbound anions in density functional calculations journal May 2011
Cooperation and Environment Characterize the Low-Lying Optical Spectrum of Liquid Water journal October 2017
Calculating Hyperfine Couplings in Large Ionic Crystals Containing Hundreds of QM Atoms: Subsystem DFT Is the Key journal October 2013
How the unit cell surface charge distribution affects the energetics of ion–solvent interactions in simulations journal September 1994
FDE-vdW: A van der Waals inclusive subsystem density-functional theory journal July 2014
Implementation of density functional embedding theory within the projector-augmented-wave method and applications to semiconductor defect states journal September 2015
Large Scale GW Calculations journal May 2015
Frozen-Density Embedding Strategy for Multilevel Simulations of Electronic Structure journal April 2015
Projection-Based Correlated Wave Function in Density Functional Theory Embedding for Periodic Systems journal March 2018
Electrostatic interaction of a solute with a continuum. Improved description of the cavity and of the surface cavity bound charge distribution. journal September 1987
Quantum Mechanical Continuum Solvation Models journal October 2005
Response to “Comment on ‘Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds’” [J. Chem. Phys. 135, 027101 (2011)] text January 2011
Electrostatics in Periodic Boundary Conditions and Real-space Corrections text January 2007
Electrostatic Interactions in Finite Systems treated with Periodic Boundary Conditions: Application to Linear-Scaling Density Functional Theory text January 2011
Semilocal and Hybrid Density Embedding Calculations of Ground-State Charge-Transfer Complexes text January 2013
FDE-vdW: A van der Waals Inclusive Subsystem Density-Functional Theory text January 2014
Electrostatics of solvated systems in periodic boundary conditions text January 2014
Determining potentials of zero charge of metal electrodes versus the standard hydrogen electrode from density-functional-theory-based molecular dynamics text January 2017
Erratum: “GW and Bethe-Salpeter study of small water clusters” [J. Chem. Phys. 144, 034109 (2016)] journal October 2016

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
Mathematics
Physics
DFT
Embedding
Periodic boundary conditions
Water