Time resolved mechanism of the isotope selectivity in the ultrafast light induced dissociation in N2

Dissociation; Electronic states; Isotopes; Molecules; Phase space methods; Wave packets; Electronic wave functions; Electronic wave packets; Non-stationary waves; Nuclear wave packet; Quantum mechanical simulations; Spin-orbit couplings; Ultrafast excitation; Vacuum ultraviolets; Wave functions

Abstract :

[en] The time evolution of a vacuum ultraviolet excited N2 molecule is followed all the way from an ultrafast excitation to dissociation by a quantum mechanical simulation. The primary aim is to discern the role of the excitation by a pulse short compared to the vibrational period, to discern the different coupling mechanisms between different electronic states, nonadiabatic, spin orbit, and to analyze the origin of any isotopic effect. We compare the picture in the time and energy domains. The initial ultrafast excitation pumps the molecule to a coherent electronic wave packet to which several singlet bound electronic states contribute. The total nonstationary wave function is given as a coherent sum of nuclear wave packets on each electronic state times the stationary electronic wave function. When the wave packets on different electronic states overlap, they are coupled in a mass-dependent manner whether one uses an adiabatic or a diabatic electronic basis. A weak spin-orbit coupling acts as a bottleneck between the bound singlet part of phase space and the triplet manifold of states in which dissociation takes place. To describe the spin-orbit perturbation that is ongoing in time, an energy-resolved eigenstate representation appears to be more intuitive. In the eigenstate basis, the singlet-to-triplet population transfer is large only between those vibronic eigenstates that are quasiresonant in energy. The states in resonance are different for different excitation energy ranges. The resonances are mass dependent, which explains the control of the isotope effect through the profile of the pulse. © 2019 Author(s).

Research Center/Unit :

MolSys - Molecular Systems - ULiège

Disciplines :

Chemistry

Author, co-author :

Komarova, Ksenia G.; Fritz Haber Center for Molecular Dynamics, Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem, 91904, Israel

Remacle, Françoise ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique

Levine, Raphaël David; Fritz Haber Center for Molecular Dynamics, Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem, 91904, Israel, Department of Molecular and Medical Pharmacology, David Geffen School of Medicine, Los Angeles, CA 90095, United States, Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, United States

Language :

English

Title :

Time resolved mechanism of the isotope selectivity in the ultrafast light induced dissociation in N2

Publication date :

2019

Journal title :

Journal of Chemical Physics

ISSN :

0021-9606

eISSN :

1089-7690

Publisher :

American Institute of Physics Inc.

Volume :

151

Issue :

Peer reviewed :

Peer Reviewed verified by ORBi

European Projects :

H2020 - 766563 - COPAC - Coherent Optical Parallel Computing

Name of the research project :

COPAC

Funders :

DOE - United States. Department of Energy
F.R.S.-FNRS - Fonds de la Recherche Scientifique
CE - Commission Européenne

Available on ORBi :

since 05 January 2020

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