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

J Chem Phys. 2013 Mar 7;138(9):094311. doi: 10.1063/1.4793215.

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 A(2)Σg(+) 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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acetylene / chemistry*
  • Cations / chemistry
  • Hydrogen / chemistry*
  • Quantum Theory*
  • Surface Properties

Substances

  • Cations
  • Hydrogen
  • Acetylene