Ultrafast hydrogen migration in acetylene cation driven by non-adiabatic effects

Mohamed Madjet, Zheng Li, Oriol Vendrell

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Non-adiabatic dynamics of the acetylene cation is investigated using mixed quantum-classical dynamics based on trajectory surface hopping. To describe the non-adiabatic effects, two surface hopping methods are used, namely, Tully's fewest switches and Landau-Zener surface hopping. Similarities and differences between the results based on those two methods are discussed. We find that the photoionization of acetylene into the first excited state A2Σ g + drives the molecule from the linear structure to a trans-bent structure. Through a conical intersection the acetylene cation can relax back to either the ground state of acetylene or vinylidene. We conclude that hydrogen migration always takes place after non-radiative electronic relaxation to the ground state of the monocation. Based on the analysis of correlation functions we identify coherent oscillations between acetylene and vinylidene with a period of about 70 fs after the electronic relaxation.

Original languageEnglish
Article number094311
JournalJournal of Chemical Physics
Volume138
Issue number9
DOIs
Publication statusPublished - 7 Mar 2013
Externally publishedYes

Fingerprint

Acetylene
acetylene
Cations
Hydrogen
cations
hydrogen
vinylidene
Ground state
Photoionization
ground state
electronics
varespladib methyl
Excited states
intersections
photoionization
switches
Switches
Trajectories
trajectories
oscillations

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry
  • Medicine(all)

Cite this

Ultrafast hydrogen migration in acetylene cation driven by non-adiabatic effects. / Madjet, Mohamed; Li, Zheng; Vendrell, Oriol.

In: Journal of Chemical Physics, Vol. 138, No. 9, 094311, 07.03.2013.

Research output: Contribution to journalArticle

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