Robust nonadiabatic molecular dynamics for metals and insulators

L. Stella*, M. Meister, A. J. Fisher, A. P. Horsfield

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Citations (Scopus)

Abstract

We present a new formulation of the correlated electron-ion dynamics (CEID) scheme, which systematically improves Ehrenfest dynamics by including quantum fluctuations around the mean-field atomic trajectories. We show that the method can simulate models of nonadiabatic electronic transitions and test it against exact integration of the time-dependent Schrodinger equation. Unlike previous formulations of CEID, the accuracy of this scheme depends on a single tunable parameter which sets the level of atomic fluctuations included. The convergence to the exact dynamics by increasing the tunable parameter is demonstrated for a model two level system. This algorithm provides a smooth description of the nonadiabatic electronic transitions which satisfies the kinematic constraints (energy and momentum conservation) and preserves quantum coherence. The applicability of this algorithm to more complex atomic systems is discussed.

Original languageEnglish
Article number214104
Number of pages15
JournalJournal of Chemical Physics
Volume127
Issue number21
DOIs
Publication statusPublished - 07 Dec 2007

Keywords

  • QUANTUM-CLASSICAL DYNAMICS
  • ELECTRON-ION DYNAMICS
  • SYSTEMS
  • TRANSITIONS
  • ENERGY
  • AVERAGES
  • SURFACES

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