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Ultrafast light-induced coupled electronic-nuclear dynamics in HCN-HNC isomers
van den Wildenberg, Stéphan; Mignolet, Benoît; Roncero-Villa, Octavio et al.
2018256th ACS National meeting
 

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Abstract :
[en] HCN is a simple molecule that undergoes several photo-induced reactions such as isomerization or photodissociation. Because of its symmetry, the molecule has a complicated electronic structure and has been the subject of numerous experimental and theoretical works. The Ground electronic state PES shows two minima that correspond to each isomer of the molecule. The two isomers are separated by an isomerization barrier. The excited electronic states of the molecule are densely packed within a band of a few eV, and several conical intersections lie at linear geometries in the Franck-Condon region of the HCN isomer. In this region, several dissociative and bound excited states cross, leading to important non-adiabatic interaction. These features make the computation of HCN photo-induced dynamics challenging because it requires a method that can suitably describe the coherent coupled dynamics of electrons and nuclei. We report on the computation of the dynamics in the electronic excited states of HCN in full dimensionality, induced by short optical pulses. We compute the dynamics by numerically integrating the nuclear TDSE on a large band of electronic excited states. The motion of nuclei on the PES of different electronic states is coupled by the Non-adiabatic coupling and by the interaction with an external electric field. The nuclear wave function is represented on a 3D spatial grid using the discrete variable representation (DVR). After the excitation, the dynamics on the excited states is probed over time using attosecond pulses photoionizing the molecule. We compute the Time-dependent Molecular Frame Photoelectron Angular Distribution (MFPAD) by representing the photoelectron wave function on a basis set of orthogonalized plane waves. The coupling with the photoionization continuum is included in the Hamiltonian using the partitioning method, and the nuclear dynamics in the cation is taken into account. We are particularly interested in probing the evolution of the electronic coherence with nuclear motion. This electronic coherence is induced by the pump pulse and is modulated by the motion of nuclei on the femtosecond timescale. The behavior of the coherence in the region of non-adiabatic coupling is not completely understood yet, in particular in multi-dimensional systems. This work constitutes a further step toward understanding and controlling photo-induced electronic coherence in molecules.
Disciplines :
Chemistry
Author, co-author :
van den Wildenberg, Stéphan ;  Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Mignolet, Benoît ;  Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Roncero-Villa, Octavio;  Consejo superior de investiogaciones scientificas > Instituto de fisica fundamental
Remacle, Françoise  ;  Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Language :
English
Title :
Ultrafast light-induced coupled electronic-nuclear dynamics in HCN-HNC isomers
Publication date :
2018
Event name :
256th ACS National meeting
Event organizer :
American Chemical Society
Event place :
Boston, United States - Massachusetts
Event date :
from 14-08-2018 to 21-08-2018
Audience :
International
Available on ORBi :
since 20 January 2020

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