[en] Few-femtosecond extreme-ultraviolet (EUV) pulses with tunable energy are employed to initiate the Jahn-Teller structural rearrangement in the ethylene cation. We report on a combined experimental and theoretical investigation of an unusual isotope effect on the low-energy competing H/D-loss and H2/D2-loss channels observed in the ultrafast dynamics induced by an EUV-pump pulse and probed by an infrared (IR) pulse. The relative production yields of C2D4+, C2D3+, and C2D2+ exhibit pronounced oscillations with a period of ∼50 fs as a function of the pump-probe delay, while the oscillatory patterns are less pronounced for C2H4+. By using surface hopping to model the nonadiabatic dynamics in the four lowest electronic states of the cation, we show that the enhanced oscillations in deuterated fragment yields arise from a synergy between the isotope effects on the wave packet relaxation through the network of conical intersections and on the vibrational frequencies of the cation.
Disciplines :
Chemistry
Author, co-author :
Lucchini, Matteo ; Department of Physics, Politecnico di Milano, 20133 Milano, Italy ; Institute for Photonics and Nanotechnologies, IFN-CNR, 20133 Milano, Italy
Murari, Mario; Department of Physics, Politecnico di Milano, 20133 Milano, Italy
Frassetto, Fabio; Institute for Photonics and Nanotechnologies, IFN-CNR, via Trasea 7, 35131 Padova, Italy
Poletto, Luca; Institute for Photonics and Nanotechnologies, IFN-CNR, via Trasea 7, 35131 Padova, Italy
Nisoli, Mauro ; Department of Physics, Politecnico di Milano, 20133 Milano, Italy ; Institute for Photonics and Nanotechnologies, IFN-CNR, 20133 Milano, Italy
Remacle, Françoise ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Language :
English
Title :
Isotope Effect on the Few-Femtosecond Relaxation Dynamics of the Ethylene Cation.
ULiège - Université de Liège COST - European Cooperation in Science and Technology F.R.S.-FNRS - Fonds de la Recherche Scientifique ERC - European Research Council
Funding number :
FNRS #T0205.20 and #T.0247.24; FNRS #2.5020.11 ,; Tomato #951224
Funding text :
This project received funding from the European Research Council (ERC): ERC Synergy Grant Agreement No. 951224, TOMATTO. F.R. and M.C.-G. acknowledge support from the Fonds National de la Recherche (F.R.S.-FNRS, Belgium) under Grants #T0205.20 and #T.0247.24, and the action of concerted research MECHANOCHEM (ARC 19/23-20, ULiege). Computational resources were provided by the Consortium des Equipements de Calcul Intensif (CECI), funded by F.R.S.-FNRS under Grant #2.5020.11 The authors thank the COST action ATTOCHEM (CA18222). F.R. and M.C.-G. thank Dr. B. Mignolet and Julie Hammoud for their useful discussions.
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