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Title: Self-interaction effects on charge-transfer collisions

Abstract

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 + + CH 4 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.

Authors:
 [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
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1357389
Alternate Identifier(s):
OSTI ID: 1353499
Report Number(s):
LLNL-JRNL-709417
Journal ID: ISSN 2469-9926; PLRAAN
Grant/Contract Number:  
AC52-07NA27344; NA0002630
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Review A
Additional Journal Information:
Journal Volume: 95; Journal Issue: 4; Journal ID: ISSN 2469-9926
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Quashie, Edwin E., Saha, Bidhan C., Andrade, Xavier, and Correa, Alfredo A.. Self-interaction effects on charge-transfer collisions. United States: N. p., 2017. Web. doi:10.1103/PhysRevA.95.042517.
Quashie, Edwin E., Saha, Bidhan C., Andrade, Xavier, & Correa, Alfredo A.. Self-interaction effects on charge-transfer collisions. United States. doi:10.1103/PhysRevA.95.042517.
Quashie, Edwin E., Saha, Bidhan C., Andrade, Xavier, and Correa, Alfredo A.. Thu . "Self-interaction effects on charge-transfer collisions". United States. doi:10.1103/PhysRevA.95.042517. https://www.osti.gov/servlets/purl/1357389.
@article{osti_1357389,
title = {Self-interaction effects on charge-transfer collisions},
author = {Quashie, Edwin E. and Saha, Bidhan C. and Andrade, Xavier and Correa, Alfredo A.},
abstractNote = {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.},
doi = {10.1103/PhysRevA.95.042517},
journal = {Physical Review A},
number = 4,
volume = 95,
place = {United States},
year = {Thu Apr 27 00:00:00 EDT 2017},
month = {Thu Apr 27 00:00:00 EDT 2017}
}

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Cited by: 3 works
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Works referenced in this record:

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  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
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Self-Consistent Equations Including Exchange and Correlation Effects
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Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
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