Transition-state theory and dynamical corrections

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

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.
Original languageEnglish
JournalPhysical Chemistry Chemical Physics
Volume4
Issue number24
Pages (from-to)5995-6000
ISSN1463-9076
Publication statusPublished - 2002

Cite this

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title = "Transition-state theory and dynamical corrections",
abstract = "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.",
author = "Henriksen, {Niels Engholm} and Hansen, {Flemming Yssing}",
year = "2002",
language = "English",
volume = "4",
pages = "5995--6000",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
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}

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

In: Physical Chemistry Chemical Physics, Vol. 4, No. 24, 2002, p. 5995-6000.

Research output: Contribution to journalJournal articleResearchpeer-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 -