### Abstract

Original language | English |
---|---|

Journal | Physical Chemistry Chemical Physics |

Volume | 4 |

Issue number | 24 |

Pages (from-to) | 5995-6000 |

ISSN | 1463-9076 |

Publication status | Published - 2002 |

### Cite this

*Physical Chemistry Chemical Physics*,

*4*(24), 5995-6000.

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*Physical Chemistry Chemical Physics*, vol. 4, no. 24, pp. 5995-6000.

**Transition-state theory and dynamical corrections.** / Henriksen, Niels Engholm; Hansen, Flemming Yssing.

Research output: Contribution to journal › Journal article › Research › peer-review

TY - JOUR

T1 - Transition-state theory and dynamical corrections

AU - Henriksen, Niels Engholm

AU - Hansen, Flemming Yssing

PY - 2002

Y1 - 2002

N2 - We consider conventional transition-state theory, and show how quantum dynamical correction factors can be incorporated in a simple fashion, as a natural extension of the fundamental formulation. Corrections due to tunneling and non-adiabatic dynamics are discussed, with emphasis on the latter. The correction factor due to non-adiabatic dynamics is considered in relation to the non-activated dissociative sticking of N-2 on Fe(111). For this process, conventional transition-state theory gives a sticking probability which is about 10 times too large (at T = 300 K). We estimate that the sticking probability is reduced by a factor of 2 due to non-adiabatic dynamics.

AB - We consider conventional transition-state theory, and show how quantum dynamical correction factors can be incorporated in a simple fashion, as a natural extension of the fundamental formulation. Corrections due to tunneling and non-adiabatic dynamics are discussed, with emphasis on the latter. The correction factor due to non-adiabatic dynamics is considered in relation to the non-activated dissociative sticking of N-2 on Fe(111). For this process, conventional transition-state theory gives a sticking probability which is about 10 times too large (at T = 300 K). We estimate that the sticking probability is reduced by a factor of 2 due to non-adiabatic dynamics.

M3 - Journal article

VL - 4

SP - 5995

EP - 6000

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 24

ER -