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. We compare many different approximations of the exchange and correlation potential, using as a test system the collision of ${\mathrm{H}}^{+}+\mathrm{C}{\mathrm{H}}_4$ at $30\mathrm{eV}$. We find that semi-local approximations, like PBE, and even hybrid functionals, like 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. From our results, we conclude that using a functional that is self-interaction free is essential to properly describe charge-transfer collisions between ions and molecules in TDDFT.

arXiv comment9 pages, 8 figures

References in corpus (13)

• Accurate and efficient algorithm for Bader charge integration
• Real-space grids and the Octopus code as tools for the development of new simulation approaches for electronic systems
• A modified Ehrenfest formalism for efficient large-scale ab initio molecular dynamics
• A time-dependent density functional theory scheme for efficient calculations of dynamic (hyper)polarizabilities
• Real-space density functional theory on graphical processing units: computational approach and comparison to Gaussian basis set methods
• Real-time electron dynamics with exact-exchange time-dependent density-functional theory
• A self-interaction-free local hybrid functional: Accurate binding energies vis-à-vis accurate ionization potentials from Kohn-Sham eigenvalues
• Electronic Band Structure Effects in the Stopping of Protons in Copper
• Universal correction for the Becke-Johnson exchange potential
• Prediction of the derivative discontinuity in density functional theory from an electrostatic description of the exchange and correlation potential
• The flexible nature of exchange, correlation and Hartree physics: resolving "delocalization" errors in a 'correlation free' density functional
• Density functional theory investigation of antiproton-helium collisions
• Optimal control theory for quantum-classical systems: Ehrenfest Molecular Dynamics based on time-dependent density-functional theory

Cited by in corpus (8)

• Exact time-dependent exchange-correlation potential in electron scattering processes
• Non-Adiabatic Approximations in Time-Dependent Density Functional Theory: Progress and Prospects
• A screened independent atom model for the description of ion collisions from atomic and molecular clusters
• Machine Learning Exchange-Correlation Potential in Time Dependent Density Functional Theory
• Electron Scattering in Time-Dependent Density Functional Theory
• Effect of chemical disorder on the electronic stopping of solid solution alloys
• The Exact Exchange-Correlation Potential in Time-Dependent Density Functional Theory: Choreographing Electrons with Steps and Peaks
• Exact time-dependent density functional theory for non-perturbative dynamics of helium atom