Importance of the lowest-lying Π electronic state in the photodissociation dynamics of LiF

In addition to the well-known 1(1)Sigma(+) and 2(1)Sigma(+) electronic states which are nonadiabatically coupled and responsible for the ionic-covalent transition in lithium fluoride (LiF), the lowest-lying Pi state is included in the present dynamical treatment. Although this purely repulsive 1(1)P...

Teljes leírás

Elmentve itt :
Bibliográfiai részletek
Szerzők: Tóth Attila
Badankó Péter
Halász Gábor
Vibók Ágnes
Csehi András
Dokumentumtípus: Cikk
Megjelent: 2018
Sorozat:CHEMICAL PHYSICS 515
Tárgyszavak:
doi:10.1016/j.chemphys.2018.05.002

mtmt:30548515
Online Access:http://publicatio.bibl.u-szeged.hu/27752
Leíró adatok
Tartalmi kivonat:In addition to the well-known 1(1)Sigma(+) and 2(1)Sigma(+) electronic states which are nonadiabatically coupled and responsible for the ionic-covalent transition in lithium fluoride (LiF), the lowest-lying Pi state is included in the present dynamical treatment. Although this purely repulsive 1(1)Pi state lies energetically close to the 2(1)Sigma(+) one and has a remarkable transition dipole moment with the 1(1)Sigma(+) ground electronic state in the Franck-Condon region, it is often excluded in studies on the photodissociation of LiF.Here we demonstrate the important role of 1(1)Pi by comparing two-state (1(1)Sigma(+) and 2(1)Sigma(+)) and three-state (1(1)Sigma(+), 2(1)Sigma(+) and 1(1)Pi) nuclear dynamical simulations focusing on the electronic state populations. Both for short (tau = 20 fs) and long (tau = 100 fs) laser pulses in the energy interval of h omega = 6.2 eV-7.35 eV we find that the population of 1(1)Pi can significantly exceed that of 2(1)Sigma(+). Furthermore we consider rotating molecules and reveal a faster dissociation compared to the case where only the vibration of the molecules are treated. (C) 2018 Elsevier B.V. All rights reserved.
Terjedelem/Fizikai jellemzők:418-426
ISSN:0301-0104