### Abstract

Original language | English |
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Article number | 184704 |

Number of pages | 9 |

Journal | Journal of Chemical Physics |

Volume | 132 |

Issue number | 18 |

Early online date | 11 May 2010 |

DOIs | |

Publication status | Published - 14 May 2010 |

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### Cite this

*Journal of Chemical Physics*,

*132*(18), [184704]. https://doi.org/10.1063/1.3424765

**Accuracy of perturbation theory for nonadiabatic effects in adsorbate-surface dynamics.** / Mizielinski, Matthew S; Bird, David M.

Research output: Contribution to journal › Article

*Journal of Chemical Physics*, vol. 132, no. 18, 184704. https://doi.org/10.1063/1.3424765

}

TY - JOUR

T1 - Accuracy of perturbation theory for nonadiabatic effects in adsorbate-surface dynamics

AU - Mizielinski, Matthew S

AU - Bird, David M

PY - 2010/5/14

Y1 - 2010/5/14

N2 - An independent-electron formalism is developed to describe the energetic distributions of hot electrons and holes excited in the interaction between an adsorbate and a metal surface. The formalism encompasses both a fully nonadiabatic treatment and a perturbation expansion in the adsorbate velocity that can be taken to arbitrary order. The widely used electronic friction and forced oscillator models are shown to be approximations of the second order perturbation result. A simple tight binding model of an atomic adsorbate interacting with a metal surface is used to demonstrate the formalism. It is shown that many orders (>10) of perturbation theory are required for quantitative agreement with fully nonadiabatic calculations of the electron and hole distribution functions. However, lower order approximations can provide a useful, semiquantitative picture of the distribution functions, and they are in good agreement with nonperturbative results for the total rate of nonadiabatic energy dissipation.

AB - An independent-electron formalism is developed to describe the energetic distributions of hot electrons and holes excited in the interaction between an adsorbate and a metal surface. The formalism encompasses both a fully nonadiabatic treatment and a perturbation expansion in the adsorbate velocity that can be taken to arbitrary order. The widely used electronic friction and forced oscillator models are shown to be approximations of the second order perturbation result. A simple tight binding model of an atomic adsorbate interacting with a metal surface is used to demonstrate the formalism. It is shown that many orders (>10) of perturbation theory are required for quantitative agreement with fully nonadiabatic calculations of the electron and hole distribution functions. However, lower order approximations can provide a useful, semiquantitative picture of the distribution functions, and they are in good agreement with nonperturbative results for the total rate of nonadiabatic energy dissipation.

UR - http://www.scopus.com/inward/record.url?scp=77952709379&partnerID=8YFLogxK

UR - http://dx.doi.org/10.1063/1.3424765

U2 - 10.1063/1.3424765

DO - 10.1063/1.3424765

M3 - Article

VL - 132

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 18

M1 - 184704

ER -