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Schlagwörter:
Isomerization; Ground states; Excited states; Non adiabatic reactions; Surface dynamics
Zusammenfassung:
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 A2Σg+ 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.
