Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Self-interaction effects on charge-transfer collisions

Journal Article · · Physical Review A
 [1];  [2];  [3];  [3]
  1. Florida State Univ., Tallahassee, FL (United States). Department of Physics; Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Quantum Simulations Group
  2. Florida State Univ., Tallahassee, FL (United States). Department of Physics
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Quantum Simulations Group
+ Show Author Affiliations
In this article, we investigate the role of the self-interaction error in the simulation of collisions using time-dependent density functional theory (TDDFT) and Ehrenfest dynamics. In addition, we compare many different approximations of the exchange and correlation potential, using as a test system the collision of H+ + CH4 at 30 eV. We find that semilocal approximations, like the Perdew-Burke- Ernzerhof (PBE), and even hybrid functionals, such as the Becke, 3-parameter, Lee-Yang-Parr (B3LYP), produce qualitatively incorrect predictions for the scattering of the proton. This discrepancy appears because the self-interaction error allows the electrons to jump too easily to the proton, leading to radically different forces with respect to the non-self-interacting case. Lastly, from our results, we conclude that using a functional that is self-interaction free is essential to properly describing charge-transfer collisions between ions and molecules in TDDFT.
Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC52-07NA27344; NA0002630
OSTI ID:
1357389
Alternate ID(s):
OSTI ID: 1353499
Report Number(s):
LLNL-JRNL--709417
Journal Information:
Physical Review A, Journal Name: Physical Review A Journal Issue: 4 Vol. 95; ISSN PLRAAN; ISSN 2469-9926
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

References (87)

Excitation energies of molecules by time-dependent density functional theory based on effective exact exchange Kohn-Sham potentials: Exchange Correlation KS Potential journal November 2002
Atomic and Molecular Processes in Controlled Thermonuclear Fusion book January 1980
Bemerkung �ber die angen�herte G�ltigkeit der klassischen Mechanik innerhalb der Quantenmechanik journal July 1927
Time-dependent density functional theory study of charge transfer in collisions journal October 2012
Non-adiabatic quantum molecular dynamics: basic formalism and case study journal September 1996
Evidence for vibrational excitation in H+ + CH4, CD4 collisions by means of a surface-hopping mechanism journal December 1975
Correlation contributions to first ionization potentials of first-row atoms, hydrides and dimers obtained with gradient corrected GGA91 density functionals journal June 1992
A density functional study of the simplest hydrogen abstraction reaction. Effect of self-interaction correction journal April 1994
Derivation and application of an accurate Kohn-Sham potential with integer discontinuity journal May 1990
Geometric derivatives of density functional theory excitation energies using gradient-corrected functionals journal January 2000
octopus: a first-principles tool for excited electron–ion dynamics journal March 2003
A fast and robust algorithm for Bader decomposition of charge density journal June 2006
Electron Removal Processes in Proton-Methane Collisions journal January 2015
A theoretical model for electron transfer in ion–atom collisions: Calculations for the collision of a proton with an argon atom journal August 2011
Exchange–Correlation Effects for Noncovalent Interactions in Density Functional Theory journal June 2016
A quantum theory of molecular structure and its applications journal July 1991
Real-Space Density Functional Theory on Graphical Processing Units: Computational Approach and Comparison to Gaussian Basis Set Methods journal September 2013
Modified Ehrenfest Formalism for Efficient Large-Scale ab initio Molecular Dynamics journal March 2009
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields journal November 1994
Density functional theory analysis of structural and electronic properties of orthorhombic perovskite CH 3 NH 3 PbI 3 journal January 2014
A new exchange–correlation functional free of delocalization and static correlation errors journal January 2014
Real-space grids and the Octopus code as tools for the development of new simulation approaches for electronic systems journal January 2015
A long-range correction scheme for generalized-gradient-approximation exchange functionals journal August 2001
Rotational excitation in the small‐angle scattering of protons from diatomic molecules journal April 1974
Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I journal October 1955
Ionization Potentials of Some Molecules journal March 1957
Propagators for the time-dependent Kohn–Sham equations journal August 2004
Quantifying the effects of the self-interaction error in DFT: When do the delocalized states appear? journal June 2005
A density-functional model of the dispersion interaction journal October 2005
About the calculation of exchange coupling constants using density-functional theory: The role of the self-interaction error journal October 2005
Many-electron self-interaction error in approximate density functionals journal November 2006
Time-dependent density functional theory Ehrenfest dynamics: Collisions between atomic oxygen and graphite clusters journal April 2007
Time-dependent density functional theory scheme for efficient calculations of dynamic (hyper)polarizabilities journal May 2007
Charge Exchange and the Theory of Ion–Atom Collisions journal October 1993
Molecular Collision Theory journal March 1976
Universal correction for the Becke–Johnson exchange potential journal January 2010
Accurate and efficient algorithm for Bader charge integration journal February 2011
Measurements of vibrational excitation of N 2 , CO, and NO by low energy proton impact journal July 1979
Vibrational state resolved measurements of differential cross sections for H + +O 2 charge transfer collisions journal September 1986
Selective vibrational excitation and mode conservation in H + +CO 2 /N 2 O inelastic and charge transfer collisions journal August 1987
Vibrationally resolved inelastic and charge transfer scattering of H + by H 2 O journal November 1987
Charge transfer and structured vibrational distributions in H + +CH 4 low‐energy collisions journal June 1988
Molecular dynamics with electronic transitions journal July 1990
Vibrationally resolved inelastic scattering and charge transfer in H + +C 2 H 2 collisions journal December 1991
A new mixing of Hartree–Fock and local density‐functional theories journal January 1993
Vibrationally resolved inelastic scattering and charge transfer in H + –C 2 H 4 collisions journal August 1993
Electron nuclear dynamics of proton collisions with methane at 30 eV journal October 1997
Plane-wave pseudopotential implementation of explicit integrators for time-dependent Kohn-Sham equations in large-scale simulations journal December 2012
A challenge for density functionals: Self-interaction error increases for systems with a noninteger number of electrons journal August 1998
The flexible nature of exchange, correlation, and Hartree physics: Resolving “delocalization” errors in a “correlation free” density functional journal January 2013
Theoretical study on collision dynamics of H + + CH 4 at low energies journal February 2014
A self-interaction-free local hybrid functional: Accurate binding energies vis-à-vis accurate ionization potentials from Kohn-Sham eigenvalues journal May 2014
Communication: Self-interaction correction with unitary invariance in density functional theory journal March 2014
Atomic partial charges on CH 3 NH 3 PbI 3 from first-principles electronic structure calculations journal April 2016
On the errors of local density (LDA) and generalized gradient (GGA) approximations to the Kohn-Sham potential and orbital energies journal May 2016
Time-Dependent Density-Functional Theory: Concepts and Applications, by Carsten A. Ullrich: Scope: monograph, textbook. Level: postgraduate, early career researcher journal February 2013
Electron correlation and the self-interaction error of density functional theory journal June 2002
Application of the time-dependent local density approximation to collision between a highly charged ion and an atom journal January 1999
Comparison of self-interaction-corrections for metal clusters journal February 2002
A grid-based Bader analysis algorithm without lattice bias journal January 2009
Time-dependent density-functional theory in massively parallel computer architectures: the octopus project journal May 2012
Optimal control theory for quantum-classical systems: Ehrenfest molecular dynamics based on time-dependent density-functional theory journal December 2013
Time-Dependent Density-Functional Theory book December 2011
Self-Consistent Equations Including Exchange and Correlation Effects journal November 1965
Exchange-correlation potential with correct asymptotic behavior journal April 1994
Excitation energies from density-functional orbital energies journal December 1995
Time-dependent mean-field description for multiple electron transfer in slow ion-cluster collisions journal May 1998
Influence of electronic exchange on single and multiple processes in collisions between bare ions and noble-gas atoms journal September 1998
Time-dependent mean-field description for multiple charge-transfer processes in Ar 8 + − Ar collisions journal November 2000
Single ionization of helium by antiprotons: A case study by self-interaction-free time-dependent density-functional theory journal September 2002
Transition Probabilities and Differential Cross Sections for Vibrational Excitation in Collisions of H + with H 2 , HD, and D 2 journal November 1973
Density-functional-theory investigation of antiproton-helium collisions journal September 2009
H + − H 2 O collisions studied by time-dependent density-functional theory combined with the molecular dynamics method journal June 2016
Self-interaction correction to density-functional approximations for many-electron systems journal May 1981
Self-interaction correction for density-functional theory of electronic energy bands of solids journal November 1983
Exact results for the charge and spin densities, exchange-correlation potentials, and density-functional eigenvalues journal March 1985
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Electronic band structure effects in the stopping of protons in copper journal October 2016
Real-Time Electron Dynamics with Exact-Exchange Time-Dependent Density-Functional Theory journal February 2008
Prediction of the Derivative Discontinuity in Density Functional Theory from an Electrostatic Description of the Exchange and Correlation Potential journal October 2011
Density-Functional Theory for Time-Dependent Systems journal March 1984
Finite-difference-pseudopotential method: Electronic structure calculations without a basis journal February 1994
Ab Initio Photoabsorption Spectra and Structures of Small Semiconductor and Metal Clusters journal July 1996
Generalized Gradient Approximation Made Simple journal October 1996
Ab Initio Excitation Spectra and Collective Electronic Response in Atoms and Clusters journal March 1999
Orbital-dependent density functionals: Theory and applications journal January 2008
Architecture of Qbox: A scalable first-principles molecular dynamics code journal January 2008

Cited By (4)

The neutron lifetime anomaly and charge exchange collisions of trapped protons journal June 2019
Exact Time-Dependent Exchange-Correlation Potential in Electron Scattering Processes journal December 2017
A screened independent atom model for the description of ion collisions from atomic and molecular clusters journal June 2018
A screened independent atom model for the description of ion collisions from atomic and molecular clusters text January 2018

Similar Records

On the phase diagram of water with density functional theory potentials: the melting temperature of Ice I-h with the Perdew-Burke-Ernzerhof and Becke-Lee-Yang-Parr functionals
Journal Article · Thu Jun 11 00:00:00 EDT 2009 · Journal of Chemical Physics, 130(22):Art. No. 211102 · OSTI ID:985015
Exchange-correlation energies of atoms from efficient density functionals: influence of the electron density
Journal Article · Sun Nov 19 19:00:00 EST 2017 · Journal of Physics. B, Atomic, Molecular and Optical Physics · OSTI ID:1413214
Mass density fluctuations in quantum and classical descriptions of liquid water
Journal Article · Sun Jun 25 20:00:00 EDT 2017 · Journal of Chemical Physics · OSTI ID:1390421

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS